AEA=3126=Durai=Venkatachala=BG

Atmospheric Environment 35 (2001) 845}858

Monitoring of PM10 and PM2.5 around primary particulate

anthropogenic emission sources
Xavier Querol *, AndreH s Alastuey , Sergio Rodriguez , Felicià Plana ,
Enrique Mantilla
, Carmen R. Ruiz
Instituto de Ciencias de la Tierra **Jaume Almera++, CSIC, C/Lluis Sole& Sabarn& s, s/n, 08028 Barcelona, Spain

Centro de Estudios Ambientales del Mediterra& neo, CEAM. Parque tecnolo& gico, C-4, sector oeste, 46980 Paterna (Valencia), Spain
Instituto de Carboqun& mica, CSIC, C/Marn& a de Luna 12, 50015 Zaragoza, Spain
Received 29 February 2000; accepted 18 July 2000

Abstract

Investigations on the monitoring of ambient air levels of atmospheric particulates were developed around a large
source of primary anthropogenic particulate emissions: the industrial ceramic area in the province of CastelloH (Eastern
Spain). Although these primary particulate emissions have a coarse grain-size distribution, the atmospheric transport
dominated by the breeze circulation accounts for a grain-size segregation, which results in ambient air particles occurring
mainly in the 2.5}10 lm range. The chemical composition of the ceramic particulate emissions is very similar to the
crustal end-member but the use of high Al, Ti and Fe as tracer elements as well as a peculiar grain-size distribution in the
insoluble major phases allow us to identify the ceramic input in the bulk particulate matter. PM2.5 instead of PM10
monitoring may avoid the interference of crustal particles without a major reduction in the secondary anthropogenic
load, with the exception of nitrate. However, a methodology based in PM2.5 measurement alone is not adequate for
monitoring the impact of primary particulate emissions (such as ceramic emissions) on air quality, since the major
ambient air particles derived from these emissions are mainly in the range of 2.5}10 lm. Consequently, in areas
characterised by major secondary particulate emissions, PM2.5 monitoring should detect anthropogenic particulate
pollutants without crustal particulate interference, whereas PM10 measurements should be used in areas with major
primary anthropogenic particulate emissions.  2001 Elsevier Science Ltd. All rights reserved.

Keywords: Atmospheric particles; PM10; PM2.5; Ceramic emissions; Ambient air quality monitoring; Primary particles; Mediterranean
basin

1. Introduction (TSP). Since an important mass fraction of TSP is made

Atmospheric particulates, especially secondary an-
thropogenic "ne particles, have been proven to have
a major impact on human health (Dockery and Pope,
1996). For many years, the atmospheric particulate stan-
dards of many countries were based on the mass concen-
tration measurement of the total suspended particles
* Corresponding author. Tel.: #34-93-4095410; fax: #34-
93-4110012.
E-mail address: xavier.querol@ija.csic.es (X. Querol).
of non-inhalable particles with a lower impact on respir-
atory and cardiovascular diseases, the relationship be-
tween health e!ects and TSP levels was found to be much
lower than the levels of atmospheric particulates "ner
than 10, 2.5 or 1 lm (PM10, PM2.5 and PM1, respec-
tively), on comparison. This was the reason for the ap-
plication of PM10 and PM2.5 measurements to the US
ambient air quality standards (US-EPA, 1987 for PM10;
US-EPA, 1996 for PM2.5). Although a decade later,
the European Union (EU) countries have followed the
same trend of replacing ambient air standards based
on TSP by PM10 standards. Currently, the incorpora-
tion of ambient air standards based on PM2.5 is also

1352-2310/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 2 - 2 3 1 0 ( 0 0 ) 0 0 3 8 7 - 3
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846 X. Querol et al. / Atmospheric Environment 35 (2001) 845}858

being considered in the EU (EU Directive 1999/30/EC, di!erent sources and simultaneous PM2.5 and PM10
1999) sampling and analysis were carried out to de"ne the best
Another important pattern of atmospheric partic- parameter for monitoring the impact of ceramic indus-
ulates, which is still not considered in ambient air stan- trial emissions on ambient air quality.
dards, is the chemical composition of TSP, PM10, PM2.5
and PM1. Major secondary acidic aerosols and hazard-
ous organic particulates are "ne-grained. Generally, in- 2. The study area
organic secondary aerosols are in the (0.5 lm (sulphate
and nitrate) and 0.5}5.0 lm (a fraction of nitrate) size The ceramic industrial areas of L'Alcora, Onda and
range (Mildford and Davidson, 1987), marine aerosol Vilareal spread along the Millars river basin from the
salts have a major fraction in the range of 1.0}5.0 lm, coast to the interior of the CastelloH Province in Eastern
whereas, primary natural particles, mainly made of Al}Si Spain (Fig. 1). The CastelloH industrial area is the second
minerals (clay minerals, quartz, feldspars) and calcium largest ceramic-producing zone in the world, accounting
and magnesium carbonates, have a major proportion in for 17% of the world's basic ceramic production
the 5}25 lm range. The carbon contents of atmospheric (600;10 m yr\). The supply of clays for the industry
particulates have a bimodal grain-size distribution with a comes mainly from an open-pit mine at a Triassic red
mode in the (2.5 lm (corresponding to anthropogenic kaolinite-rich clay deposit in Sant Joan de MoroH (east of
organic particles) and '10 lm (corresponding to mineral the city of L'Alcora, Fig. 1) and from the Cretaceous
carbonates). Primary anthropogenic particulate emissions kaolinite-rich deposits in the province of Teruel. In a mi-
are also usually in the '2.5 lm range. nor proportion, a large variety of other natural and
At a global scale, the anthropogenic emissions do synthetic products, such as feldspars, melting phases and
not exceed the 10% of the global particulate emissions,
whereas the natural primary emissions reach the 84%
(2.9;10 t yr\, after Kiehl and Rhode, 1995; IPCC,
1996). Concerning the global anthropogenic particulate
emissions, the secondary aerosols exceed the primary
particulate emissions (0.26;10 and 0.11;10 t yr\).
Consequently, the global emissions of natural partic-
ulates are mainly primary, whereas, the anthropogenic
emissions are predominantly secondary.
Future trends for particulate monitoring strategies
tend to monitor PM2.5 rather than PM10 because of its
more direct relationship with health e!ects and to avoid
natural particulate interference. However, industrial ac-
tivities with high primary particulate emissions, such as
cement, concrete, ceramics or the mining sectors, may
have a great impact on the ambient air quality due to
their intensive particulate emissions in the 2.5}10 lm
range. Moreover, these emissions usually have a chemical
composition similar to that of natural crustal emissions
(high Ca, Al, Si, Fe, K proportions), which impedes the
appropriate monitoring of ambient air particulate levels.
This paper introduces the results obtained from a re-
search project supported by the Spanish Ministry of the
Environment and the CICYT (ComisioH n Interministerial
de Ciencia y TecnologmH a) to develop source apportion-
ment analyses of PM10 and PM2.5 focussed on the
speci"c atmospheric and geographical characteristics of
Spain. The present study focuses on the evaluation of the
physico-chemical patterns of ambient air particulate
matter in ceramic industrial zones. In these areas, al-
though high levels of secondary particulates may be
emitted, the largest source contribution in high partic-
ulate events is due to primary emissions of mineral mat-
ter from atomiser plants and fugitive emissions from Fig. 1. Location of major ceramic production areas and "xed
piling stock. Continuous grain-size analysis of TSP from sampling stations for PM10/PM2.5 measurements.
 Aea=3126=Durai=VVC
X. Querol et al. / Atmospheric Environment 35 (2001) 845}858
colourants, are also broadly consumed. The kaolinite-
rich material is "nely ground in the atomisers, which
produces a homogeneous "ne powder ((63 lm). This
process coupled with the large clay consumption
(20;10 t in 1998) and the large fugitive emissions from
the storage, handling and transport of the clay, probably
accounts for the largest fraction of the local anthropo-
genic particulate emissions.
Secondary particulate emissions from the manufactur-
ing of glass and enamel may account more for the emis-
sion of hazardous atmospheric trace pollutants than for
their signi"cant contribution to the bulk particulate
emissions. Other particulate emission sources such as
intensive road transport, frequent biomass combustion
from intensive orange tree cropping, and marine aero-
sols, must also be considered.
This puzzling particulate-emission setting is placed in
a complex Mediterranean atmospheric environment. The
intensive convective dynamics, the breeze circulation,
the low rainfall rate, the highly mineralised soils and the
frequent occurrence of high particulate Sahara air-mass
intrusions further complicate the monitoring of the an-
thropogenic particulate emissions impact on ambient air
quality. The study was made in July because of the large
impact of some of the previously mentioned atmospheric
environmental factors on the particulate levels.
In summer, the North Atlantic anticyclone becomes
reinforced over the northern latitudes. Weak-gradient
conditions on the Iberian Peninsula and strong ground
heating give rise to the development of the Iberian ther-
mal low (ITL), due to thermally induced local and meso-
scale circulations, such as sea breeze, up-slope winds and
convective cells (MillaH n et al., 1991).
The study area (Fig. 1) includes the CastelloH alluvial
plain (La Plana) which is limited on the north by the
Palmes mountain chain (6}7 km from the coast) and
includes Mt. Bartolo as its highest peak (780 m.a.s.l.). The
Millars basin, with an approximate E}W direction, con-
verges with the "rst range of mountains at 20 km from
the coast.
The movement of the air masses over the eastern Coast
of the Iberian Peninsula as well as the evolution of the
boundary layer are strongly linked to its complex top-
ography. During the daytime the sea breeze is channelled
Table 1
Location of the "xed monitoring and sampling stations
Sampling site Location
Mt. Bartolo Telecom antenna peak
Onda Monitoring station (urban background station)
Vilareal Post o$ce (urban background station)
Grau Monitoring station (urban background station)
L'Alcora Council house (urban background station)
847
along the bottom of the valleys up to 60}80 km inland,
whereas at the top of the mountains and valley slopes
a combination of sea breeze and up-slope winds gives rise
to a chimney e!ect, injecting air from low levels to alti-
tudes ranging from a few hundred meters up to 2}3 km.
The anticyclonic subsidence and the dynamics formation
of the sea breeze cells favour the formation of reservoir
layers of secondary pollutants (thermally separated be-
tween themselves by inversions) in the return #ow mov-
ing toward the Mediterranean Sea. A compensatory
sinking over the sea, due to thermal buoyancy over the
warmed terrain and anticyclonic subsidence, reinforces
the sea-breeze circulation and prepares the reservoir
layers over the sea for re-entrance a few days later.
During the evening and night, the solar-activated circula-
tions cease, and a reversal in the breeze takes place.
Thus, the sea-breeze circulation in summer favours
good ventilation conditions in the valleys but scarce
air-mass renovation, due to the above-described re-circu-
lations of the air masses (MillaH n et al., 1997), resulting
in a potential atmospheric reservoir e!ect for secondary
air pollutants in the Western Mediterranean.
3. Methodology
3.1. Sampling sites
The following sampling and measurement sites (Fig.
1 and Table 1) were selected based on the distribution of
the major emission sources (marine, rural, urban and
industrial sites) and on the atmospheric-circulation pecu-
liarities of the study area:
The Grau station is located in a rural or semi-urban
area, which is sporadically in#uenced by the industrial
and urban plumes, especially the plume from CastelloH in
night-breeze conditions.
The station of the Villareal city is an urban site in the
lower watercourse of the Millars, situated 10 km from the
coastline, in the centre of a zone of a large ceramic-
industrial activity. This station is under the in#uence of
both urban (mainly tra$c) and industrial emissions. Dur-
ing the daytime period this location is situated leeward of
the city and the ceramic emissions with respect to the
Latitude Longitude
4030509N 0030153W
3935743N 0031543W
3935634N 0030625W
3935859N 0030031W
4030509N 0030153W
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848 X. Querol et al. / Atmospheric Environment 35 (2001) 845}858

characteristic breeze #ow. For this reason, the contribu-

tions due to tra$c emissions should be equal or more
important than the industrial emissions. On the other
hand, the in#uence of the ceramic emissions are expected
to predominate during the nocturnal breeze period.
The Onda station is a suburban background station
near the city of Onda, situated in an open area, 20 km
from the coastline, without direct in#uence from urban
or road tra$c activities. It is situated on the leeward
of the nearby ceramic industries, and in sea-breeze
conditions it is also in#uenced by the coastal industrial
emissions.
The L+Alcora station is located in an urban background
site in the municipality of L'Alcora, in the most produc-
tive ceramic zone of CastelloH . In the daytime the breeze
drags the atmospheric emissions with a northwestern
transport, whereas in the nocturnal breeze phase the
previously emitted particulates travel seawards towards
L'Alcora.
Finally, the Mt. Bartolo station is located at the top of
the Mt. Bartolo peak. Possible anthropogenic emissions
could come from a nearby residential area and from
various roadways concentrated on the coastal fringe. The
objective of using this emplacement was to provide a ver-
tical gradient for discriminating possible high-altitude
Fig. 2. Correlation of PM10 and PM2.5 measurements between
contributions not present at lower levels. the GRIMM laser spectrometer and the high-volume sampler.
Lastly, meteorological data from the air quality net- Solid lines indicate 1:1, dashed line is the correlation line. In
work cabins of Ermita and Penyeta and the meteorologi- PM10, correlation was performed at the following sites: (1) Solid
cal towers of Cirat, Rambla of the Viuda and Borriana circles, suburban Onda station; (2) Solid triangles, rural Mona-
were also used to carry out the interpretations. grega station; (3) Triangles, urban Barcelona station; (4) Squares,
urban L'Hospitalet station. PM2.5 correlation was performed at
3.2. Sampling and measurements Onda (2 samples) and L'Hospitalet.

The sampling of atmospheric particulate matter was

carried out by means of high-volume samplers (DH-80
and MCV-CAF, 30 m h\) equipped with PM10 and
PM2.5 DIGITEL and MCV cut-o! inlets and quartz
glass "lters (QF20 Schleicher and Schuell). Daily samp-
ling was made from 12 to 23 July 1999 at the "ve "xed
monitoring stations (Table 1). Furthermore, sampling of
TSP grain-size fractions (seven stages from 0.3 to
'20 lm) was performed for 4 days (from 11 to 23 July
1999) at the Onda station by means of a Retsch PI-1
cascade impactor.
Once the levels of bulk particulates were obtained by
weighting the "lters using standard procedures, one-half
of each of them (PM10 and PM2.5) plus the insoluble
fractions of the di!erent stages of the cascade impactor
(previously "ltered with MQ cellulose membrane "lters)
and blank "lters were digested following the method of
Querol et al. (1998). The soluble fraction of 1/4 of
each "lter and the di!erent grain-size stages obtained
with the cascade impactor were extracted with distilled
water at 803C. The last 1/4 of each "lter was used
to directly determine the total C content by LECO
methodology.
The solutions obtained were analysed by: (a) induc-
tively coupled plasma-atomic emission spectrometry
(ICP-AES) for major elements, (b) capillary electrophor-
esis (CEF) for anions, and (c) colorimetry-#ow injection
analysis (FIA) for NH>. The digestion of blank "lters

with 2}3 mg of NBS-1633a reference material was used to
ensure analysis quality for the same levels of the sample
digestion concentrations. Relative analytical errors were
between 3 and 10% for the elements studied.
Automatic measurements of atmospheric particulate
levels and grain-size distribution were performed with
the laser spectrometer dust monitor GRIMM 1108
(Labortechnik GmbH & Co. KG) at the "xed and mobile
stations. This dust monitor permits the determination
of particulate levels in 15 di!erent grain-size channels
from 0.3 to '20 lm. The accuracy of the GRIMM-1108
measurements was checked, before, during and after the
"eld campaigns, by comparing the levels of simultaneous
daily PM10 and PM2.5 measurements obtained with the
standard gravimetric methodology. Fig. 2 shows good
agreement between the PM10 measurements obtained
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X. Querol et al. / Atmospheric Environment 35 (2001) 845}858 849

Table 2
Location of mobile station for grain-size analysis of TSP with the GRIMM laser spectrometer around the major emission sources (E)
and ambient air measurements (A)

No. Measurement description Longitude Latitude

E-1 Fugitive emissions from a clay mine 00 06 31 W 40 04 39 N

E-2 Fugitive emissions from clay transport at L'Alcora 00 10 08 W 40 03 00 N
E-3 Atomiser, Onda 00 14 35 W 39 58 18 N
E-4 Atomiser L'Alcora 00 10 29 W 40 03 29 N
E-4b Atomiser L'Alcora second measurement 00 10 29 W 40 03 29 N
E-5 Around stack emissions PA factory 00 04 50 W 39 57 38 N
E-6 Around stack emissions SA factory 00 09 11 W 40 02 36 N
E-7 Around stack emissions VE factory 00 14 49 W 39 58 11 N
E-8 Around stack emissions JM factory 00 04 21 W 39 57 51 N
E-9 Around stack emissions JM factory second measure 00 04 20 W 39 57 56 N
E-10 Around stack emissions EG factory 00 09 35 W 39 56 41 N
E-11 Around stack emissions NA factory 00 13 07 W 39 57 41 N
E-12 Around stack emissions POR factory 00 05 38 W 40 01 21 N
E-12b Emission plume measurement POR factory 00 05 38 W 40 01 21 N
E-13 Emission plume measurement PA factory 00 04 41 W 39 57 22 N
E-14 Dense tra$c crossroad at CastelloH 00 02 14 W 39 59 22 N
E-15 Dense tra$c crossroad at CastelloH 00 03 19 W 39 58 19 N
E-16 Emission plume from petrochemical plant 00 01 06 W 39 57 06 N
E-17 Biomass "ring around orange tree plantations 00 01 03 W 39 59 36 N
E-18 Marine aerosols Borriana harbour (Morro) 00 04 13 W 39 51 32 N
E-19 Marine aerosols Millars delta 00 00 49 W 39 54 22 N
E-20 Marine aerosols Ben Afali beach 00 00 15 W 39 55 20 N
E-20b Marine aerosols Ben Afali beach on the shoreline 00 00 15 W 39 55 20 N
A-1 Northern background levels around the ceramic zone 00 16 10 W 39 59 10 N
A-2 Middle background levels in orange plantations 00 09 44 W 39 59 09 N
A-3 Coastal background levels leeward of ceramic emissions 00 04 03 W 39 54 45 N
A-4 Urban background levels L'Alcora 00 11 20 W 40 04 02 N
A-5 Semi-urban background levels L'Alcora (St. Salvador) 00 11 49 W 40 05 11 N
A-6 Urban background levels L'Alcora 00 12 30 W 40 04 10 N
A-7 Semi-urban background levels L'Alcora}Onda 00 10 46 W 39 59 29 N
A-8 Semi-urban background levels Millars bridge 00 07 11 W 39 57 54 N
A-9 Rural-remote background levels Mt. Bartolo 00 01 53 W 40 05 09 N

with the high-volume sampler and the GRIMM-1108
laser spectrometer. Although good agreement was also
obtained in the two simultaneous PM2.5 measurements
during the "eld campaign, a longer inter-comparison
demonstrated that the GRIMM 1108 measurements
were 15% lower than those obtained by the gravimetric
method (Fig. 2).
The measurements of particulate-matter levels and
grain-size distribution with the laser spectrometer were
carried out in the vicinities of the following emission
sources (Table 2 and Fig. 3):
1. Di!erent types of ceramic emission plumes including
those from enamel (white to yellow plumes) and tile
(reddish plumes) factories and atomiser centres. Fugi-
tive emissions were measured at a certain distance of
a number of sources including the stockpiles in the
atomiser centres, the largest open-pit mine in the area,
and a crossroad where high emissions from the short
road transport between the clay-mining area and the
tiling and atomising centres were evident.
2. The tra$c emissions in the vicinity of a crossroad with
high tra$c density (mainly cars) at two di!erent sites
inside the city of CastelloH .
3. The marine aerosol at three di!erent coastal sites (a
few metres from the shoreline) in the in-land breeze
circulation stage.
4. The biomass combustion emissions were measured at
di!erent distances from the "res in extensive orange-
tree plantations located upwind from the ceramic
emissions in the Grau area.
5. The emission plume from the petrochemical plant was
detected with the help of the SO analysers in a COS-

PEC unit and, subsequently, grain-size measurements
were obtained without interference of the ceramic
emissions in the in-land breeze stage.
 Aea=3126=Durai=VVC
850 X. Querol et al. / Atmospheric Environment 35 (2001) 845}858
Fig. 3. Location of mobile measurement stations for grain-size
analysis of TSP with the GRIMM laser spectrometer around the
major emission sources (E) and ambient air measurements (A).
See detailed data of location in Table 2.
In addition to the emission measurements, short
(1}2 h) measurements were performed in background
areas up- and down-wind of the emission plumes from
the ceramic zones (Table 2 and Fig. 3). The measure-
ments were performed in the in-land breeze stage follow-
ing a cross-section from the shoreline (backwards to the
petrochemical and ceramic emissions), downwind of
the petrochemical emission and "nally downwind of the
ceramic emission plumes. Short measurements were also
carried out at di!erent background sites in#uenced by
di!erent ceramic emission sources.
Longer measurements (24 h) were carried out at the
Grau, L'Alcora and Onda stations to study the grain size
range of atmospheric particulates in#uenced by the ce-
ramic emissions transported by the breeze circulation.
4. Results and discussions
During the measurement campaign typical summer
meteorological conditions predominated with a local-
circulation dominance in the measuring zone, in spite of
the fact that a smooth perturbation aloft took place at
the end of the "rst week. Thus, the scenario consisting
of a daytime inland and a nocturnal seaward #ow was
repeated daily in the Millars Valley during the measure-
ment campaign. The typical summer thermal vertical
structure with subsidence inversions was also observed.
4.1. PM10 and PM2.5 levels
As expected, the lowest PM10 mean values were ob-
tained at the Mt. Bartolo background station
(18 lg m\). The highest PM10 values were registered at
the L'Alcora and Vilareal stations (56 and 44 lg m\,
respectively) which are located in the most productive
ceramic areas. The Grau and Onda stations, located in
rural or suburban areas, which are temporarily in-
#uenced by the emission plumes, have intermediate
PM10 values of approx. 30 lg m\. The mean PM2.5
fraction of PM10 in the study area was approx. 50%wt,
whereas the mean PM10 fraction of total suspended
particles (TSP) was found to be approx. 65%, with ex-
treme mean daily values from 50 to 80 wt%.
The levels of marine aerosols were homogeneously
distributed in the study area as deduced from the narrow
variations in the concentrations of Na>, Cl\ and Mg>
observed among the di!erent sampling sites (Table 3).
A similar homogeneous pattern was observed for levels
of sulphate and ammonium (Table 3). The background,
the suburban and the industrial stations showed mean
levels ranging only from 7 to 9 lg m\ for anthropogenic
sulphate and 2.1}2.8 lg m\ for ammonium. The ionic
balance between ammonium and sulphate demonstrates
that around 80% of the anthropogenic sulphate is pres-
ent as ammonium sulphate. The occurrence of am-
monium sulphate, sodium chloride and magnesium
probably in discrete background aerosols probably ac-
counts for the homogeneous levels of these phases in
PM10 across the study area.
Conversely, the nitrate levels were considerably higher
at the Vilareal site (with the highest tra$c density) and
lower, by a factor of 4}5, at the rural background site of
Mt. Bartolo (Table 3). A similar pattern was also ob-
served for the distribution of levels of organic carbon
and phosphor. The other stations registered intermediate
values for nitrate and organic carbon with the excep-
tion of the suburban Grau station. The frequent uncon-
trolled biomass combustion from intensive orange tree
cropping around this station probably accounted for the
high levels of organic carbon, phosphor and nitrate,
similar to those recorded at the heavily polluted Vilareal
site.
The levels of the major elements emitted by the ce-
ramic industry (clay-related elements such as Si, Al, Fe,
K and Ti) were one order-of-magnitude higher at the
L'Alcora and Vilareal stations than at the Bartolo site,
with the Onda and Grau stations having intermediate
levels (Table 3). Levels of Ca and Mg, mainly from soil
emissions with a low proportion from the ceramic indus-
try, also increased in the ceramic zone with respect to the
background site but in a lower rate than the ceramic-
related elements.
On an average, the addition of all the constituents
determined reached 90% of the bulk PM10 or PM2.5
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X. Querol et al. / Atmospheric Environment 35 (2001) 845}858 851

Table 3
Mean daily major elements, carbonates, ammonium, organic#elemental carbon and bulk PM10 levels obtained at Mt. Bartolo, Grau,
Onda, Vilareal and L'Alcora sampling sites

Location Bartolo Grau Onda Vilareal L'Alcora

N 5 9 11 9 2
CO\(lg m\) 0.7 2.0 1.6 3.5 4.3

Org#Elem C (lg m\) 2.9 6.1 3.9 6.8 5.5
SiO (lg m\) 1.1 2.7 3.6 6.0 12.0

Al O (lg m\) 0.4 1.1 1.4 2.4 4.8
 
Ca (lg m\) 0.5 1.3 1.0 2.3 2.9
K (lg m\) 0.2 0.5 0.5 0.8 1.5
Mg (lg m\) 0.2 0.3 0.2 0.4 0.4
Fe (lg m\) 0.2 0.4 0.4 0.7 1.2
NO\ (lg m\) 0.9 2.9 1.8 3.5 1.8

NH> (lg m\) 1.9 2.5 2.3 2.1 1.9

SO\ no marine (lg m\) 7.0 8.4 8.7 9.0 8.4

SO\ marine (lg m\) 0.2 0.3 0.2 0.4 0.2

Na (lg m\) 0.8 1.2 1.0 1.4 0.9
Cl\ (lg m\) 0.2 0.8 0.4 0.9 0.5
R major elements (lg m\) 17 31 27 41 48
PM10 gravimetry (lg m\) 19 36 32 44 56
Determined (%) 91 85 85 94 86
Crustal (%) 19 27 33 40 58
Secondary (%) 57 45 47 37 27
Org#Elem C (%) 17 20 14 17 12
Marine A (%) 7 8 6 7 4

N, number of daily samples. The results of the source apportionment analysis including crustal sources, secondary particulates
(ammonium sulphate and nitrate), organic#elemental carbon, and marine aerosols are also reported as the percentage of contribution
of each source with respect to the bulk PM10 levels.

levels obtained by the gravimetric method. The results
indicate that the mean marine aerosol input represents
between 4 (L'Alcora) and 8 (Grau) wt% of the bulk
PM10 levels (Table 3). The proportion of organic and
elemental carbon, mainly proceeding from combustion
processes, is relatively homogeneously distributed across
the study area with values from 12 to 20% wt of bulk
PM10, with the highest values being recorded for the
Grau and Vilareal sites (Table 3). The PM10 proportion
from the crustal input (both soil and ceramic emissions)
ranged from 18% of bulk PM10 at the Bartolo site, up to
40}55 wt% in the ceramic productive area. The Onda
and Grau sites have intermediate proportions (around
30 wt%). Finally, the proportion of secondary inorganic
aerosols (ammonium, sulphate and nitrate) is very high at
the background site (near by 60% of bulk PM10 levels)
and the Onda and Grau sites (45}50 wt%), whereas in the
ceramic zone (Vilareal and L'Alcora) it is much lower
(approx. 30 wt%), the background origin of ammonium
sulphate in the study area. Thus, in the rural background
site, these external phases account for most of the par-
ticulate fraction, whereas this proportion is drastically
reduced in the ceramic zone, where local input pre-
dominates.
Levels of Pb and Zn also reached high values in the
ceramic zone (around 0.4 lg m\) but very low levels at
the rural background site (0.05 lg m\, Table 4). Al-
though the levels of the other elements were relatively
low, with the exception of As (up to 25 ng m\) and Cr
(up to 7 ng m\) at L'Alcora and Vilareal, the spatial
variation of levels of As, Cr, Cs, Pb, Rb, Sr, Ti, V, Zn and
Zr suggests a chie#y ceramic origin for these elements
(Table 4). However, Ba, Cd, Co, Cu, Ga, Hf, Mn, Mo, Nb,
Ni, Sb, Sc, Sn, Th, U and Y do not show any relationship
with ceramic emissions (Table 4). The last conclusion
demonstrates that the well-known relationship between
some ceramic activities and the high levels of Hf, U and
Th in atmospheric particles has a very local incidence.
Analysis of simultaneous samples of PM10 and PM2.5
has evidenced that the crustal and marine loads are
strongly reduced in the PM2.5 with respect to the PM10
(Table 5) measurements. In contrast, most of the second-
ary anthropogenic phases are trapped by the PM2.5
sampling, with the exception of nitrate which registers
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852 X. Querol et al. / Atmospheric Environment 35 (2001) 845}858

Table 4 Table 5
Mean daily trace element levels in PM10 obtained at Mt. Bar- Comparison between levels of major and trace elements, carbon-
tolo, Grau, Onda, Vilareal and L'Alcora sampling sites (N, ates, ammonium, organic#elemental carbon in PM10 and
number of daily samples) PM2.5, simultaneously sampled at Onda

Location Bartolo Grau Onda Vilareal L'Alcora Onda 21}22/07/1999 22}23/07/1999

PM10 PM2.5 PM10 PM2.5

N 5 9 11 9 2
CO\ (lg m\) 4.6 4.4 5.7 4.6
As (ng m\) 1 5 8 11 25 
Org#Elem C (lg m\) 2.1 1.2 2.2 0.4
Ba (ng m\) 1 11 6 16 21 SiO (lg m\) 5.1 2.3 4.9 0.7
Cd (ng m\) 0.1 0.7 0.4 0.6 0.9 
Al O (lg m\) 2.0 1.2 2.1 0.5
Co (ng m\) 0.4 0.3 0.6 0.6 1.1  
Ca (lg m\) 1.4 0.8 1.4 0.2
Cr (ng m\) 0.6 1.7 2.2 3.6 6.9 K (lg m\) 0.6 0.5 0.7 0.4
Cs (ng m\) 0.1 0.3 0.4 0.5 1.2 Mg (lg m\) 0.3 0.1 0.3 0.1
Cu (ng m\) 77 36 6 39 88 Fe (lg m\) 0.5 0.3 0.6 0.2
Ga (ng m\) 0.1 0.1 0.2 0.2 0.5 NO\ (lg m\) 1.3 0.5 1.4 0.4
Hf (ng m\) 0.2 0.4 0.4 0.5 0.4 
NH> (lg m\) 1.9 1.8 2.1 2.0
Mn (ng m\) 5 7 7 11 13 
SO\ no marine (lg m\) 6.8 6.1 7.1 6.7
Mo (ng m\) 0.6 0.6 0.8 2.9 2.2 
SO\ marine (lg m\) 0.2 0.1 0.2 0.1
Nb (ng m\) 0.1 0.1 0.1 0.2 0.3 
Na (lg m\) 0.8 0.3 0.8 0.2
Ni (ng m\) 5 3 4 7 9 Cl\ (lg m\) 0.3 0.2 0.5 0.2
P (ng m\) 15 50 32 52 42
Pb (ng m\) 45 199 285 346 341 R major elements (lg m\) 28 20 31 17
Rb (ng m\) 1 1 2 3 6 PM10/2.5 gravimetry (lg m\) 33 23 37 17
Sb (ng m\) 1 2 1 2 2 Determined (%) 87 90 84 100
Sc (ng m\) 0.1 0.1 0.1 0.2 0.3
Crustal (%) 43 33 41 16
Sn (ng m\) 1 2 1 2 2
Secondary (%) 36 42 35 54
Sr (ng m\) 2 4 4 6 10
Org C (%) 16 22 19 27
Th (ng m\) 0.7 0.6 0.2 0.9 0.2
Marine A (%) 5 3 5 3
Ti (ng m\) 12 29 34 65 111
U (ng m\) (0.1 0.2 0.6 (0.1 (0.1 As (ng m) 10 10 10 7
V (ng m\) 8 7 7 10 14 Ba (ng m) 8 3 9 2
Y (ng m\) 0.1 0.2 0.1 0.3 0.4 Cd (ng m) 0.6 0.5 0.6 0.4
Zn (ng m\) 54 132 178 264 699 Co (ng m) 0.5 0.2 0.5 0.1
Zr (ng m\) 3 8 11 12 21 Cr (ng m) 2.0 1.5 2.1 1.0
La (ng m\) 0.2 0.3 0.4 0.6 1.1 Cs (ng m) 0.5 0.4 0.5 0.3
Ce (ng m\) 0.2 0.7 0.9 1.3 2.2 Cu (ng m) 10 9 10 10
Tb (ng m\) 0.03 0.03 0.03 0.03 0.03 Hf (ng m) 0.3 0.1 0.1 0.3
Tm (ng m\) 0.03 0.03 0.02 0.03 0.02 Mn (ng m) 7 5 8 3
Yb (ng m\) 0.02 0.04 0.05 0.04 0.06 Mo (ng m) 0.3 0.2 (0.1 (0.1
Nb (ng m) 0.2 0.1 0.2 0.1
Ni (ng m) 3 3 3 3
P (ng m) 33 22 32 12
only 40% of the PM10 nitrate levels. As it will be demon- Pb (ng m) 354 330 368 245
strated later, the occurrence of calcium and sodium ni- Rb (ng m) 3 2 3 1
trate in the 2.5}5.0 lm range probably accounts for the Sb (ng m) 1 1 1 1
lower nitrate measurements in the PM2.5 "lters. Sn (ng m) 1 1 1 1
Sr (ng m) 5 2 6 1
Th (ng m) (0.1 (0.1 0.5 (0.1
4.2. Cascade impactor Ti (ng m) 48 28 51 14
U (ng m) (0.1 (0.1 (0.1 (0.1
Ammonium and ammonium}calcium sulphates are V (ng m) 6 5 7 7
Zn (ng m) 197 186 204 170
mainly concentrated in the "nest fractions (0.3}0.7
Zr (ng m) 8 4 8 5
and 0.7}1.0 lm, respectively). These two "ne fractions
account for 80% of the bulk anthropogenic sulphate The results of the source apportionment analysis including crustal
(Fig. 4). The coarser sulphate is mostly present as calcium sources, secondary particulates (ammonium sulphate and nitrate), or-
ganic#elemental carbon, and marine aerosols are also reported as the
and sodium sulphates. percentage of contribution of each source with respect to the bulk
The marine aerosol phases are mainly concentrated in PM10/2.5 levels.
the 3}10 lm fraction as inferred from the Na> distribu-
tion (Fig. 4). However, there is a clear grain-size segrega-
tion between the occurrence of NaCl (6}10 and '10 lm nitrate (originally present in the (6 lm fraction) re-
fractions) and the NaNO ((6 lm fraction). This is due acts with sodium chloride to give rise to ammonium

to the well-known Na>}NO\}Cl\}NH> interaction chloride (gas) and sodium nitrate. The ionic balance also
 
(Harrison and Pio, 1983; Wall et al., 1988). Ammonium indicates the occurrence of Ca(NO ) in the '6 lm

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X. Querol et al. / Atmospheric Environment 35 (2001) 845}858
Fig. 4. Grain-size distribution of weekly levels of the soluble
fraction of major species (neq m\) and selected trace metals
(ng m\) in total suspended particles obtained at Onda from 12
to 23 July 1999.
fraction probably due to nitri"cation of soil particles
(Harrison and Kito, 1990) and NH NO in the (1.5 lm
 
fraction (Fig. 4).
As expected, SO\, NO\, Cl\, NH>, Ca, Mg, Mn, Pb,
   occurrence of "ne grain sizes for these elements and the
V and Zn have a major soluble fraction (Fig. 4), and Al,
K, Sr, Ba, Cr, Cu, Ni, Ti and Fe are mainly present in
insoluble phases (Fig. 5). Insoluble soil and ceramic par-
ticulates such as clay minerals, calcium carbonate and
feldspars (crustal phases) showed a bi-modal grain-size
distribution with modes occurring in the 1.5}6.0 and
'25 lm fractions as deduced from the grain-size distri-
bution of insoluble levels of Ca, Al, K and Fe (Fig. 5).
Soluble fractions of Mn, Fe, V and Cr, probably occur-
ring in di!erent oxide phases with an anthropogenic
origin, are mostly in the 6}10 lm range (Figs. 4 and 5).
However, Pb and Zn mainly occur in the soluble very
"ne grain-size fraction, '85% of bulk Pb levels occur-
ring in the PM2.5 fraction (Fig. 4).
853
Fig. 5. Comparison of the grain-size distributions of weekly
levels of the insoluble fraction of major elements and selected
trace metals in total suspended particles obtained at Onda in
this study with that of a typical urban distribution obtained in
Barcelona. Levels in ng m\.
Unusually high proportions of insoluble levels of Al,
Ca, Na, Sr, S, P and Fe were found in the "ne grain-size
modes ((1.5 lm) when compared with a normal urban
or industrial grain-size distribution (Fig. 5). This atypical
unusually high proportion of insoluble Na levels (up to
30% of bulk Na) are probably the result of the condensa-
tion of volatile emissions from high temperature pro-
cesses developed in the enamel manufacture. These pecu-
liar patterns may be a good tool for tracing the input of
ceramic emissions on bulk PM10 levels, since the bulk
chemical patterns, characterised by high Al, Si, Fe and
Ca levels, are similar to the soil end-member.
4.3. Grain-size distribution of atmospheric particulates
around the emission sources
The fugitive emissions from the largest open-pit clay
mine in the area induced very high ambient air PM10
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854 X. Querol et al. / Atmospheric Environment 35 (2001) 845}858

Table 6
Mean daily major elements, carbonates, ammonium, organic#elemental carbon and bulk PM10 levels obtained at Mt. Bartolo, Grau,
Onda, Vilareal and L'Alcora sampling sites. N, number of daily samples . Levels in lg m\

TSP PM10 PM7.5 PM5 PM2.5 PM1.0 PM0.8

Ceramic emissions
Fugitive emissions
Clay mine E-1 823 337 266 163 61 9 7
Transport E-2 1770 704 560 340 185 21 15
Atomiser-ATESA E-3 387 113 97 75 43 11 9
Atomiser-L'A E-4 420 128 108 78 40 10 8
Atomiser-L'A2 E-4b 532 214 187 137 74 16 12
Around stack emissions
PA E-5 349 251 223 159 83 21 16
SA E-6 127 56 49 38 22 6 5
VE E-7 353 170 158 157 150 126 120
JM E-8 78 38 35 30 24 12 11
JM-2 E-9 83 44 40 38 35 24 23
EG E-10 135 64 59 49 33 12 10
NA E-11 267 84 75 68 57 22 17
POR E-12 483 218 188 142 84 21 16
Direct measurements of plume emissions
POR E-12b 855 385 330 247 144 33 25
PA E-13 2485 1018 867 610 289 47 34
Tra$c emissions
CastelloH -1 E-14 62 42 35 26 17 8 7
CastelloH -2 E-15 47 27 26 23 19 9 8

Combustion emissions
Petrochemical E-16 25 22 21 19 15 7 6
Biomass E-17 149 73 58 43 28 13 12
Marine aerosols
Borriana E-18 36 31 29 24 17 7 6
Millars E-19 53 44 42 33 20 7 6
Ben Afeli-1 E-20 86 49 43 35 24 8 7
Ben Afeli-2 E-20b 31 28 27 25 19 7 6
Ambient air measurements at background sites
Cross-section
North-ceramic A-1 55 35 32 28 22 12 12
Middle A-2 39 24 23 22 21 11 10
Coastal A-3 28 24 23 21 17 9 8
L'Alcora-1 A-4 91 46 42 33 22 8 8
L'Alcora-2 A-5 62 41 36 29 20 9 8
L'Alcora-3 A-6 66 43 37 27 16 7 6
L'Alcora}Onda A-7 33 24 22 18 15 8 7
Millars bridge A-8 62 43 40 34 27 14 13
Mt. Bartolo A-9 32 25 24 21 16 8 7

The results of the source apportionment analysis including crustal sources, secondary particulates (ammonium sulphate and nitrate),
anthropogenic organic#elemental carbon, and marine aerosols are also reported as the percentage of contribution of each source with
respect to the bulk PM10 levels.

levels around the mining area (approx. 300 lg m\ were (40 wt%). As expected, this coarse grain-size distribution
recorded on an hourly basis, Table 6 and Fig. 6), but the (high and low modes of '20 and 4}15 lm, respectively)
PM2.5 fraction was relatively low (22 wt% of the PM10). was similar to that previously described for the clay-
The PM10 fraction also represented a low TSP fraction related elements (Al, K, Fe) obtained from the cascade
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X. Querol et al. / Atmospheric Environment 35 (2001) 845}858
Fig. 6. Selected cases of grain-size distribution of hourly levels of total suspended particles measured in the vicinities of the major
ceramic emission sources. Levels in lg m\. See codes in Table 6 and Fig. 3 for location of measurement sites.
impactor measurements. The grain-size distribution of
ambient air particulates around di!erent clay atomisers
and from several crossroads with high densities of clay
road-based transport was also very similar (Fig. 6
and Table 6), with a major proportion in the '20 lm
and two secondary modes occurring in the 4}7.5 and
10}15 lm fractions. The PM10 levels around these sites
also reached very high levels (from 120 to 700 lg m\ on
an hourly basis). The percentages of PM10 over TSP and
PM2.5 over PM10 were constantly low (from 30 to
45 wt% and from 40 to 45 wt%, respectively) around the
four atomisers. Although the TSP grain size pattern was
slightly "ner around the atomisers when compared with
the fugitive emissions from clay mining and transport,
the similarity of these grain-size distributions suggests
that the major emission source from these activities is the
fugitive emissions from the large clay stockpiles and
transport.
PM10 levels around 10 ceramic factories including
tiling and enamel factories were signi"cantly lower than
around the mining, atomiser and clay-transport sources
(Table 6 and Fig. 6). Levels ranging from 40 to
250 lg m\ of PM10 on an hourly basis were obtained
around these ceramic factories which emit particulate mat-
ter mainly through small-stacks. The percentage of PM10
over TSP and PM2.5 over PM10 increased considerably
with respect to the previous emission sources. Although
a similar percentages of PM10 over TSP was determined
for both tiling and enamel factories (from 50 to 65 wt%),
the enamel sources were characterised by a higher propor-
tion of "ne particles (from 80 to 95 wt% of PM10 were in
the PM2.5 range) with respect to the tiling factories
(60}70 wt% of PM10 were in the PM2.5 range).
The grain-size distribution of tra$c particulate emis-
sions was measured at di!erent places of the study area
including major crossroads in the ceramic zone and in
855
the city of CastelloH . Under typical summer conditions,
direct tra$c emissions did not give rise to high PM10
ambient air levels. PM10 levels of 30}40 lg m\ on an
hourly basis were obtained around major crossroads
inside the city of CastelloH (Table 6). The percentage of
PM10 over TSP ranged between 60 and 65 wt%, whereas
the PM2.5 fraction over PM10 ranged from 45 to 70 wt%
(Fig. 7).
Intermediate PM10 ambient air levels (around
70 lg m\ of PM10 for a 1/2 h basis) were obtained in
areas with intensive biomass combustion activities
around large orange-tree plantations. However, the high
density of biomass "res could make this emission type
a very important source for PM10 in the study area. In
the vicinity of the "res the percentage of PM10 over TSP
was approx. 50 wt%, whereas the PM2.5 fraction over
PM10 reached only 40 wt% (Table 6 and Fig. 7).
Measurements of the marine aerosols obtained at dif-
ferent sites of the shoreline in periods with a dominant
daytime in-land breeze #ow, showed PM10 levels from
25 to 50 lg m\ of PM10 (on an hourly basis). The
percentage of PM10 over TSP was constantly around
85 wt% and the PM2.5 fraction over PM10 ranged from
45 to 75 wt%. Constant levels of 5}8 lg m\ were mea-
sured for fractions (0.8 lm (Table 6 and Fig. 7) which
coincide with the levels and the grain size distribution
obtained for ammonium sulphate phases with the cas-
cade impactor.
Measurements were also made in the plume of the
petrochemical plant located on a coastal site at the south
of the city of CastelloH . PM10 levels were relatively low
(approx. 20 lg m\ hourly PM10) compared with the
other anthropogenic source. The grain-size distribution
was very similar to that of the marine aerosols, with levels
of "ne secondary particles similar to those of the back-
ground marine measurements (Fig. 7).
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856 X. Querol et al. / Atmospheric Environment 35 (2001) 845}858

Fig. 7. Selected cases of grain-size distribution of hourly levels of total suspended particles measured in the vicinities of non-ceramic
emission sources. Levels in lg m\. See codes in Table 6 and Fig. 3 for location of measurement sites.

Fig. 8. Grain-size distribution of hourly levels of total suspended particles measured in rural-remote (Bartolo Mt.) and semi-urban
(Alcora, Onda) background areas. Levels in lg m\. See codes in Table 6 and Fig. 3 for location of measurement sites.

4.4. Grain-size distribution of atmospheric particulates:
ambient air measurements
One set of measurements was performed following
a cross-section from the coastal area towards the ce-
ramic-producing zones during the daytime in-land breeze
circulation stage (Table 6). The measurements were per-
formed in background rural and suburban areas and
showed a clear trend of an increase in the particulate
levels from the coastal area (20 lg PM10 m\ and 15 lg
PM2.5 m\) towards the ceramic area (36 lg PM10 m\
and 25 lg PM2.5 m\). The "nest fraction (mainly
(0.8 lm sulphate) also followed the same trend (from
8 to 12 lg m\). All the measurements of this cross-
section also showed two grain-size modes of around
1.6}3.0 and 5.0}7.5 lm, corresponding to marine aero-
sols. However, there is a marked trend to increase pro-
gressively the 5.0}7.5 lm mode (Fig. 8), probably due to
the increase in nitrate levels and primary ceramic partic-
ulates towards the ceramic zone. In addition to these
modes, two additional coarse particulate inputs are evi-
dent (in the 10}15 and '20 lm) as the ceramic area is
approached (Fig. 8). These grain size patterns and levels
were also constantly recorded by a number of additional
measurements performed at ceramic background sites
around L'Alcora and Onda (Table 6 and Fig. 8).
The results of the measurements performed on the
rural background station of Mt. Bartolo evidenced levels
of PM10 around 25 lg m\, of which 1/3 proceed
from the ammonium sulphate phases (8 lg m\ in the
(0.8 lm fraction). In addition to other possible partic-
ulate inputs such as nitrates and crustal particles, the two
other modes (2}3 and 5}7.5 lm) identi"ed were coinci-
dent with the bi-modal distribution of the marine aerosol
(Fig. 8). The presence of relatively high levels of am-
monium sulphate at this site during the daytime breeze
stage supports the high re-circulation of this secondary
phase.
In summer, the emission plumes from the ceramic
zones are dragged by the nocturnal seaward breeze which
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X. Querol et al. / Atmospheric Environment 35 (2001) 845}858
Fig. 9. Time evolution of levels of di!erent grain-size fractions
of atmospheric particulates in the daily breeze cycle at the Grau,
Onda and L'Alcora monitoring stations. Levels in lg m\. The
simultaneous wind speed and direction measurements are also
included to show the breeze dynamics observed during the
measuring period.
accounts for a rise of the nighttime coastal particulate
levels. 24 h measurements with semi-hourly particulate
levels performed at the Grau station demonstrated that
in the daytime stage all grain-size fractions remained at
relatively low levels due to the relatively clean marine air
mass #ows (see levels of particles and wind velocity and
direction in Fig. 9). Later, in the nocturnal stage (21}7 h)
the PM10 levels increased drastically as a consequence of
857
the seaward transport of pollutants from the ceramic
area (Fig. 9). However, the levels of PM1 and PM2.5 did
not exhibit major changes during the daily cycle, with the
2.5}10 lm fractions being responsible for the increase
in PM10 levels (Fig. 9). Because of the longer transport
of pollutants, the increase in the '10 lm fraction regis-
tered close to the ceramic emission sources (Onda) was
not recorded at the Grau station.
The high impact of 2.5}10 lm particles on bulk PM10
levels is also evidenced by the measurements performed
at L'Alcora. At this site, high levels of PM25 and PM10
are reached during the daytime stage, when local ceramic
emissions are relatively high. At this stage the emission
plumes are dragged towards the northwestern areas by
the inland breeze circulation. Subsequently, in the noc-
turnal period, these high particulate air masses travel
back to the emission-source area due to the seaward
breeze. These processes account for the higher PM10
levels reached during the nocturnal stage with respect to
the daytime stage (Fig. 9). Because of the breeze transport
and consequent grain-size segregation, nocturnal levels
of '10 lm particles are low when compared with the
daytime stage. Once more it becomes very evident that
the grain-size range which detects the impact of these
polluted air masses on the ambient air quality is that of
2.5}10 lm (Fig. 9). The two major PM10 peaks registered
between 21}22 and 7}8 h (both local time, see Fig. 9)
probably mark the calm periods produced during the
change in wind direction between the breeze stages.
A similar situation was found at the Onda station
where the impact of emission plumes from the nearby
ceramic emission sources is not as important as in
L'Alcora, but the nocturnal breeze circulation also ac-
counts for high 2.5}10 and '10 lm particulate levels.
The PM2.5 levels did not evidence the impact of these
plumes at all (Fig. 9). The calm periods between breeze
stages are also evidenced in the late evening and early
morning by high particulate events (Fig. 9).
5. Conclusions
Although the ceramic primary particulate emissions
from the CastelloH area have a coarse grain-size distribu-
tion, the particulate transport dominated by the breeze
circulation accounts for a subsequent grain-size segrega-
tion. Thus, major impacts on the ambient air quality of
the coastal area induced by the particulate ceramic emis-
sions occur in the nocturnal period due to the seaward
transport of polluted air masses. Levels of ambient air
particles increase mainly in the 2.5}10 lm range due to
grain-size segregation by transport.
The chemical composition of the ceramic particulate
emissions is very similar to the crustal end-member
but high Al, Fe and Ti levels coupled with a peculiar
grain-size distribution in the major insoluble phases
 Aea=3126=Durai=VVC
858 X. Querol et al. / Atmospheric Environment 35 (2001) 845}858
allows us to identify the ceramic input in the particulate
matter.
Although replacement of PM10 by PM2.5 measure-
ments in ambient air quality monitoring standards is
a likely trend for the future, the PM2.5 is not an adequate
parameter for monitoring the impact of primary partic-
ulate emissions (such as ceramic emissions) on air quality,
since the major particulate ambient air levels are in the
range of 2.5}10 lm.
As demonstrated from the analysis of major and trace
elements in simultaneous PM10 and PM2.5 sampling
and cascade impactor and from the Grimm measure-
ments, PM2.5 measurement avoids the interference of
crustal particulates without major reduction in the sec-
ondary anthropogenic load with the exception of nitrate.
However, occasionally industrial primary particulate
emissions may have the crustal particulate grain-size, and
consequently these emissions will not be detected by
PM2.5 measurements. From a technical point of view,
the measurement of atmospheric particulates has to be
speci"c for monitoring areas with major secondary or
primary particulate emissions. In areas characterised by
major secondary particulate emissions, PM2.5 monitor-
ing should detect anthropogenic particulate pollutants
without crustal particulate interference, whereas PM10
measurements should be used in areas with major pri-
mary anthropogenic particulate emissions.
Acknowledgements
The present study has been supported by the Plan
Nacional de I#D of the Spanish CICYT, project
AMB98-1044, and by the Spanish Ministry of the Envir-
onment. We would like to express our gratitude to the
DireccioH General de EducacioH i Qualitat Ambiental of
the Generalitat Valenciana for supplying the data from
the monitoring stations and for their interest in the develop-
ment of this study.
References
Dockery, D., Pope, A., 1996. Epidemiology of acute health
e!ects: summary of time-series studies. In: Wilson, R.,
Spengler, J.D. (Eds.), Particles in Air: Concentration and
Health E!ects. Harvard University Press, Cambridge, USA,
pp. 123}147.
EU Directive 1999/30/EC, 1999. Council directive relating to
limit values for sulphur dioxide, nitrogen dioxide and oxide
of nitrogen, particulate matter and lead in ambient air. The
Council of the European Union.
Harrison, R.M., Pio, C., 1983. Size di!erentiated composition of
inorganic aerosol of both marine and polluted continental
origin. Atmospheric Environment 17, 1733}1738.
Harrison, R.M., Kito, A.M.N., 1990. Field inter-comparison of
"lter pack and denuder sampling methods for reactive gas-
eous and particulate pollutants. Atmospheric Environment
24A, 2633}2640.
IPCC, 1996. Climate change. In: Houghton, J.T., Meira Filho,
L.G., Callander, B.A., Harris, N., Kattenberg, A., Maskell, K.
(Eds.), The Science of Climate Change. Cambridge Univer-
sity Press, Cambridge, UK, 584pp.
Kiehl, J.T., Rhode, H., 1995. Modelling geographical and sea-
sonal forcing due to aerosols. In: Charlson, R.J., Heintzen-
berg, J. (Eds.), Aerosol Forcing of Climate. Wiley, New York,
pp. 281}296.
Mildford, J.B., Davidson, C.I., 1987. The sizes of particulate
sulphate and nitrate in the atmosphere: a review. Journal of
Air Pollution Control Association 37 (2), 125}134.
MillaH n, M.M., Artin ano, B., Alonso, L., Navazo, M., 1991. The
e!ect of meso-scale #ows on regional and long-range atmo-
spheric transport in the Western Mediterranean area. Atmo-
spheric Environment 25A (5/6), 949}963.
MillaH n, M.M., Salvador, R., Mantilla, E., 1997. Photooxidant
dynamics in the Mediterranean basin in summer: results
from European research projects. Journal of Geophysical
Research 102 (D7), 8811}8823.
Querol, X., Alastuey, A., Puicercus, J.A., Mantilla, E., Ruiz, C.R.,
LoH pez-Soler, A., Plana, F., Juan, R., 1998. Seasonal evolution
of suspended particles around a large coal-"red power sta-
tion: chemical characterisation. Atmospheric Environment
32 (11), 719}731.
US-EPA, 1987. Second addendum to air quality criteria for
particulate matter and sulfur oxides (1982): assessment of
newly available health e!ects information. Research Triangle
Park, EPA Report 600/8-86-020F, NTIS PB87-176574.
US-EPA, 1996. Air quality criteria for particulate matter.
EPA/600/P-95/001F, US Environmental Protection Agency,
Washington, DC.
Wall, S.M., John, W., Ondo, J.L., 1988. Measurement of aerosol
size distribution for nitrate and major ionic species. Atmo-
spheric Environment 22, 1649}1656.