Atmospheric Environment 45 (2011) 6777e6787

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Atmospheric Environment
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Sources and variability of inhalable road dust particles in three European cities
F. Amatoa, *, M. Pandolfia, T. Morenoa, M. Furgerb, J. Peya, A. Alastueya, N. Bukowieckib,
A.S.H. Prevotb, U. Baltenspergerb, X. Querola
a
Institute of Environmental Assessment and Water Research, Spanish Research Council (IDÆA-CSIC), C/Jordi Girona 18e26, 08034 Barcelona, Spain
b
Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen, Switzerland

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

Article history: Despite their importance, current scientific knowledge on non-exhaust emissions by road traffic is scarce,
Received 8 March 2011 severely hampering a reliable description of these particles in atmospheric dispersion models. Conse-
Received in revised form quently, it is still very difficult to convincingly evaluate population exposure to traffic-related compo-
25 May 2011
nents in large cities, especially given the significant variation in traffic-related air pollution
Accepted 1 June 2011
concentrations on a small scale (e.g. within 100e1000 m of a busy road). One factor contributing to this
uncertainty is the lack of a reliable emission estimate for vehicular non-exhaust emissions. Emissions
Keywords:
vary from location to location due to the impact of climate, road surface characteristics and traffic
PM10
Traffic
conditions, but the geographical coverage for which Emission Factors are available and the amount of
Non-exhaust knowledge regarding the variability within a city environment are very limited.
Source apportionment The present study investigates the spatial and chemical properties of the strength of the emission
PM10 source (road dust particles below 10 mm) in three contrasting European urban environments: two
Mineralogy Spanish cities (Barcelona and Girona), and a Swiss city (Zürich). Loadings of road dust <10 mm from the 8
Emissions sites sampled in Zürich ranged from 0.2 to 1.3 mg m
2, the lowest loadings of the study. The minimum
PMF loadings in Girona (Spain) were as high as the maximum in Zürich, with a range of 1.3e7.1 mg m
2. By far
the most polluted site in terms of road dust <10 mm mass loading is Barcelona (Spain), where a range of
3.7e23.1 mg m
2 was recorded in the city center samples. Four main sources were found to drive the
variability of road dust particles <10 mm: Mineral (road wear and urban dust generated mostly by
construction emissions), Motor Exhaust, Brake wear and Tire wear. Road wear/Mineral is the dominating
source in Spanish cities (w60%), but represents only 30% of road dust loadings in Zürich where contri-
butions are more equally distributed among the four main sources of road dust. Regardless of the city
categories loadings of OC, EC, Fe, Cr, Mn, Cu, Zn, Mo, Sn, Sb, Cs, Ba, W, Pb and Bi (mg m
2) increase by
a factor of 1.2e2.2, from streets with <15 kveh to streets with 15e40 kveh day
1. At highly trafficked
sites (>40 kveh day
1) loadings were again increasing by a further factor of 2.6e10.1. Finally, agreement
was found between the composition of sampled materials and the composition (available from litera-
ture) of PM10 material emitted by vehicles via resuspension (both in Zürich and Barcelona). This
permitted to find a relationship, potentially able to calculate emission factors from known amount of
deposited pollutants in those cities/environment where no real-world EFs are available from literature.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction European legislation for the protection of human health (2008/50/

As a result of the demographic growth of large European cities,
urban air pollution has become increasingly affected by traffic-
related emissions in recent years. Emissions of inhalable particu-
late matter (PM) from road traffic are responsible for most of the
exceedances of the Air Quality Limit Values established by the
* Corresponding author.
E-mail address: fulvio.amato@idaea.csic.es (F. Amato).
EC; EEA, 2010). The daily (50 mg m
3) and annual (40 mg m
3) limit
values of PM10 (atmospheric particles with mean aerodynamic
diameter <10 mm) concentrations in ambient air are in fact
exceeded mostly in the urban areas (EEA, 2010). These standards
derive from the epidemiological and toxicological evidence of
increased risks of mortality and cardiovascular and respiratory
diseases due to an increase of ambient concentrations of PM
(Dockery et al., 1993; Dockery and Pope, 1994; Peters et al., 2001;
Brunekreef and Holgate, 2002; Brunekreef and Forsberg, 2005;
Pope and Dockery, 2006). Although the PM components causing

1352-2310/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2011.06.003
6778 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787
the health impacts have not been identified unequivocally, recent
studies have identified traffic-related particles as suspect (Hoek
et al., 2002). A large part of the road traffic emissions comes from
the so-called non-exhaust sector. This comprises several mechan-
ical processes that emit PM while vehicles are traveling, including
wear of brakes, tires and road pavement but mainly involving the
resuspension of deposited particles due to wheel-generated
turbulence (Schauer et al., 2006; Thorpe and Harrison, 2008;
Tervahattu et al., 2006; Raisanen et al., 2005; Kupiainen et al.,
2003, 2005; Kupiainen and Tervahattu, 2004). Several studies
have shown that the importance of these non-exhaust emissions is
comparable (or even higher) to that of emissions from vehicle
exhaust systems (Querol et al., 2001a, 2004; Harrison et al., 2008;
Amato et al., 2009a; Bukowiecki et al., 2010). The environmental
burden of the non-exhaust emissions is high for several reasons:
i) brakes and road dust particles may contain toxic and carcinogenic
components such as heavy metals, PAHs and sulphides (IARC, 1989;
Schauer et al., 2006); ii) due to their coarse-size (above 2.5 mm),
non-exhaust particles have a large impact on the PM mass and
therefore are responsible of most of the exceedances measured in
cities (Umweltbundesamt, 2006; EEA, 2010); iii) concern over this
PM component is increasing because while a downward trend for
the exhaust emissions is being achieved through the EUROx stan-
dards applied over the last decade (2007/715/EC; 2002/51/EC
among others), no abatement strategies are currently underway
to combat non-exhaust emissions. Despite their importance,
however, current scientific knowledge on non-exhaust emissions
by road traffic is scarce, severely hampering a reliable description of
these particles in atmospheric dispersion models. Such dispersion
models are key tools in Air Quality research and management,
although current urban scale models typically fail in reproducing
PM10 concentrations in large cities. The reason for this is often
attributed to the fact that non-exhaust emissions from road traffic
are not implemented in the models. Consequently, it is still very
difficult to convincingly evaluate population exposure to traffic-
related components in large cities, especially given the significant
variation in traffic-related air pollution concentrations on a small
scale (e.g. within 100e1000 m of a busy road). One factor
contributing to this uncertainty is the lack of a reliable estimate of
Emission Factors (EFs) for vehicular non-exhaust emissions. Emis-
sions vary from location to location due to the impact of climate,
road surface characteristics and traffic conditions, but the
geographical coverage for which EFs are available and the amount
of knowledge regarding the variability within a city environment
are very limited (e.g. Schaap et al., 2009).
The present study aims to investigate the spatial and chemical
properties of road sediments below 10 mm in three contrasting
European urban environments: a densely populated major coastal
Mediterranean city (Barcelona, Spain; 1.6 million inhab.), a much
smaller Southern European city situated away from the coast
(Girona, Spain: 95,000 inhab.), and a moderate sized Central
European city (Zürich, Switzerland: 380,000 inhab.). The same
sampling method, protocol and laboratory analysis was applied for
the three campaigns, in order to minimize technical and experi-
mental uncertainties.
2. Methodology
2.1. Sampling locations
This study involved sampling in three cities, one in Switzerland
(Zürich) and two in NE Spain (Barcelona and Girona), with each
locality being chosen for having very different demographic,
weather and pollution patterns from the other two (Fig. 1). Zürich
is the largest city and economic center of Switzerland with
Fig. 1. Cities under study.
a population of 380,000 within an area of 92 km2 (rising to well
over 1 million if the wider metropolitan area is included). Despite
the existence of a good public transport system, many people
choose to drive to and from work, resulting in a traffic movement of
130,000 cars/workday into town. Heavy duty vehicles (HDV)
represent 6% of traveling vehicles and only 13% of cars are diesel
powered. During winter, the city applies rock salt (NaCl) as de-icer,
but due to the relatively warm weather of February 2008, in the
week before and during our sampling campaign no salt was applied
to the roads. The city of Girona in NE Spain has a population of
around 95,000, and although of significant size it is not large
enough to have developed a transport infrastructure involving
metro, light railway or tram, and abundant road traffic (20% HDV,
43% of cars are diesel powered) is a major cause of local atmo-
spheric contamination. There are no important point sources of
heavy industrial contaminants. In the case of Barcelona, the densely
populated and traffic-clogged urban nucleus of the city has around
1.6 million inhabitants (4 millions in the greater Metropolitan
Area), making it the second most populated city in Spain. The
density of road traffic assumes great importance to any study of
urban pollution in Barcelona, having around one million vehicles
(62% of which are cars, 45% diesel powered) and one of the highest
car density in Europe (6.100 veh km
2, 15% HDV).
A total of 39 samples were obtained from the three cities. 23 of
them were collected in the city centers in order to characterize the
typical average conditions of each city: 8 in Zürich, 9 in Barcelona
and 6 in Girona. 16 extra samples were collected in special interest
sites of Barcelona, but outside the city center: ring roads, harbor
and construction sites.
Evidently road dust levels are not constant in time: the issue
whether measured loads were representing the typical equilibrium
value between deposition and re-entrainment, for a consistent
comparison between the different cities, needs to be discussed. As
suggested by several authors (Pitt, 1979; Alley and Smith, 1981;
Grottker, 1987; Hall and Hamilton, 1991), after a rain event, road
dust loads tend to increase with time until a steady state is reached.
These authors found that the number of days necessary to reach
the steady state (i.e. the equilibrium road dust level) varies
considerably from one to several weeks, depending mostly on the
road surface type. The starting time of each campaign was then
planned to be at least 7 days after a rain event: thus in Barcelona
sampling was performed in June 2007, after 21 dry days, in Zürich
 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787
in February 2008, after 14 dry days, and in Girona in July 2008, after
7 dry days.
2.2. Sampling
The study of road dust resuspension has been usually
approached by collecting samples directly from road pavement by
sweeping sediments and either sieving (Ho et al., 2003; Manno
et al., 2006; Han et al., 2007) or inducing resuspension in the
laboratory and extracting PM10 through size selective inlets (Zhao
et al., 2006; Chow et al., 2004). Generally these procedures and
sample treatments are affected by the loss of fine particles owing
basically to the difficulties of collecting all deposited material and
also to the electrostatic adhesion of particles to pincer/brush hairs
and sieve meshes. In order to reduce such losses during the
sampling procedure and given the absence of a definitive sampling
protocol, a new sampling device for road dust <10 mm was devel-
oped within this work. A field resuspension chamber was developed
for this special purpose directly vacuuming in situ, at an air flow rate
of 25 l min
1, the resuspended fraction <10 mm of road dust onto
filters (Amato et al., 2009b). Road sediments are vacuumed from the
pavement of active traffic lanes, using a Becker rotative pump
powered by a Honda field generator (located always at some
distance downwind with respect to the sampling area). Particles are
immediately resuspended in a methacrylate deposition chamber
and the particles small and/or light enough to be carried by the air
current continued their journey through the system (Figure S1).
These particles enter a Negretti stainless steel elutriation filter
designed to only allow passage to particles <10 mm. The particles
able to penetrate this barrier are finally collected on 47 mm diam-
eter fiber quartz or Teflon membrane filters, while particles with
aerodynamic diameter >10 mm are deposited in the methacrylate
chamber and along the elutriation filter. Electrostatic adhesion
might cause some losses of particles <10 mm. Nevertheless, this loss
is likely to be negligible with respect to losses of traditional
sampling procedures (i.e. sweeping). In any case the chamber
sediments are brought to laboratory, dried for 48 h at room
temperature, sieved and then analyzed by means of a MALVERN
MASTERSIZER Particle Sizer with the aim of verifying the size
selection of the sampling system. The Particle Sizer is based on the
principle of laser ensemble light scattering and employs two forms
of optical configuration: the conventional Fourier optics and the
reverse Fourier optics that permits to extend the measurement size
range down to 0.1 mm. Results showed that fraction <10 mm was in
average only 0.6% and 0.1% (in volume) of samples previously sieved
at 250 mm and 63 mm, respectively.
Earlier road dust studies have not quantified the load of mass
(mg m
2) collected at different sites (probably because of the
absence of a sampling protocol) with the result that very little is
known about the spatial and temporal variability of road dust
<10 mm. Moreover, the material should be collected from an active
lane of the road, which is difficult in practice because the active part
of the road is occupied by moving vehicles (Venkatram, 2000).
In this study, sampling was performed at all sites in a compa-
rable surface area of one square meter (1 m2) for 30 min (Fig. 2).
For each location, three different square meters were sampled
using three different filters to reduce casual errors and to collect
enough sample for the required analyses: two quartz fiber filters
of 47 mm diameter Munktell were used to determine the loading
of major and trace elements, OC and EC and one Teflon 47 mm
diameter membrane filters (1 mm pore) Schleicher & Schuell to
determine the loading of water-soluble ions. Using our method it
was then possible to quantify the load of road dust <10 mm per
unit area and through the chemical speciation, also of road dust
6779
Fig. 2. Sketch of sampling area for PM10 material.
components <10 mm (OC, EC, metals, sulfate, nitrate, chloride and
ammonium).
2.3. Characterization of samples
Before sampling, quartz fiber filters (Ø47 mm) were dried at
205  C during 5 h and conditioned for 48 h at 20  C and 50% of
relative humidity. Teflon filters (Ø47 mm) were conditioned under
the same conditions but without previous drying. Weights of blank
filters were measured three times every 24 h by means of a Sarto-
rius LA 130 S-F microbalance (1 mg sensitivity). After weighing,
filters were kept in PETRI holders. After sampling, filters were
brought back to laboratory, weighted two more times every 24 h of
conditioning at the same ambient conditions of first weighing.
Once the weights of samples were determined, filters were
destined to several analytical (destructive) treatments. The proce-
dure is briefly listed below, more details are available in Amato et al.
(2009b):
- Quartz fiber filters were acid digested (5 ml HF, 2.5 ml HNO3,
2.5 ml HClO4) for the determination of trace and major
elements and analyzed respectively by inductively coupled
plasma mass spectrometry and atomic emission spectrometry
(ICP-MS and ICP-AES) (Querol et al., 2001b). Within each
digestion of a batch of samples the Standard Reference Mate-
rialÒ 1633b Coal Fly Ash was used to assure a satisfactory
recovery yield of elements analyzed by ICP-MS and ICP-AES.
- Teflon membrane filters and/or Quartz fiber filters were
leached in 20 ml of bi-distilled water for the extraction of
water-soluble ions and subsequent analysis by ion chroma-
tography (IC) for sulfate, nitrate and chloride and by specific
electrode for ammonium.
- A section of 1.5 cm2 from a quartz fiber filter was used for the
determination of OC and EC by a thermaleoptical transmission
technique (Birch and Cary, 1996) using a Sunset Laboratory
OCEC Analyzer with the NIOSH 5040 temperature program.
Total carbon (TC) was determined as the sum of OC and EC.
- Teflon membrane filters were used for determining content of
Silica by means of X-ray fluorescence (XRF), following the
methodology of Raman et al. (2008).
6780 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787
In every case blank loadings were subtracted for determining
final loadings in samples.
Mineralogy of samples was investigated by means of XRD
analyses on a second batch of samples collected simultaneously to
the first one. Due to the high mass sample required for XRD anal-
ysis, these samples were not particles <10 mm but total sediments,
collected by pincer brushing on the gutter zone. The objective of
these analyses was to determine the major minerals present in road
sediments, so that the loss of fine (under detection limit) metallic
particles was accepted. XRD analyses were performed in a Bruker
D-5005 diffractometer. Results were obtained using CuKa radiation,
a wavelength of l ¼ 1.5405 Å and a secondary graphite mono-
chromator. Analytical conditions were step size of 0.05 (with 3 s
timing per step), 40 kV and 30 mA.
2.3.1. Source apportionment
The investigation of sources responsible for road sediments
build-up in each city was carried out by means of a Positive Matrix
Factorization (PMF, Paatero and Tapper, 1994). PMF is a least
squares factor analysis based on mass conservation principle
X
p
xij ¼ gik fjk i ¼ 1; 2; .; m j ¼ 1; 2; .; n
k¼1
to assist in identification of sources and their contributions to
observed pollutant loadings. In equation (1), xij is the jth species
loading measured in the ith sample, gik is the contribution of the
kth source to the ith sample, fjk is the loading of the jth species in
the kth source and eij is the residual associated with the jth
species loading measured in the ith sample. The standard PMF
model was extended by means of the Multilinear Engine
programming language (ME-2; Paatero, 1999) in order to add
specific physical constraints (e.g. the sum of a single source
profile cannot exceed the unity). The loading of road dust per
square meter was introduced as independent variable (mg m
2),
while loadings of road dust components (mg m
2) were the
dependent variables.
Chemical species for PMF analysis were selected based on the
signal to noise ratio (Paatero and Hopke, 2003), the percentage of
values above detection limit and to the database size requirements.
Individual uncertainties of data were estimated following the
approach of Amato et al. (2009a). There are several sources of
uncertainty contributing to the overall one: the ones associated
with the analytical determination, the one of the air volume
sampled, the deviation from the sampling convention etc. The
uncertainty associated with the analytical procedure is likely to be
one of the most important sources of uncertainty. For this reason it
was experimentally determined using a similar methodology than
the one described by Thompson and Howarth (1976), obtaining
a functional relationship between amount of analyte and its cor-
responding uncertainty. The equation chosen for fitting these
results was:
s2a ¼ s20 þ ða$mÞ2
where sa is the uncertainty associated with analytical procedure, m
is the mass of analyte in the filter while s0 and a are fitting
parameters. This equation has been already applied to PMF (Anttila
et al., 1995) and shows a satisfactory theoretical basis (Thompson,
1988). In addition, the analytical determination includes also the
subtraction of blank filters which, due to the destructive nature of
the analysis, were different filters from the sampled ones and for
each batch of samples. This causes an additional source of uncer-
tainty sBLK that has to be propagated jointly with sa to obtain the
analytical determination uncertainty sA:
s2A ¼ s2a þ s2BLK
In order to include additional sources of uncertainty a part from
the analytical ones, the overall uncertainty was expanded by the
following formula
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 ffi
s2ij ¼ s2A þ b$xij 2
being b a coefficient that was estimated to be 0.15 which might
accounts for the error in the flow rate and other additional sources
of uncertainty. The uncertainty estimate provides a criterion to
separate the species which retain a significant signal from the ones
dominated by noise.
Factors are classified taking into account several diagnostic
criteria: i) PMF-resolved chemical profile; ii) the variation
explained for every species by each factor (specific tracers can be
identified); iii) the spatial evolution of contributions.
3. Results and discussion
Sampling sites and main average results are shown in Table 1.
Loadings of road dust <10 mm from the 8 sites sampled in Zürich
(1)
range from 0.2 to 1.3 mg m
2, with an average of 0.7  0.3 mg m
2,
making this site the least contaminated (in terms of road dust) of
the 3 under study. The loading range in Girona starts where the one
of Zürich ends, with a range of 1.3e7.1 mg m
2 and an average of
3.5  2.4 mg m
2. The construction site of Pompeu Fabra in Girona
had highly anomalous mass loadings (48.7 mg m
2) and these were
not included within the average (Table 1). By far the most polluted
site in terms of road dust <10 mm mass loading is Barcelona, where
a range of 3.7e23.1 mg m
2 and an average of 8.9  6.5 mg m
2
were recorded.
Interestingly, the lowest loading was found at the site (6)
where we could observe the pavement was clearly renovated.
Although we do not have information on pavement ages/mainte-
nance at the rest of sites, it is worth to mention that there are
several possible properties of a new pavement that might affect
road dust loading. More bitumen in the road surface will reduce
the sampling efficiency by gluing dust to the sticky surface. A new
pavement also might have a smoother surface with lower macro
texture which may result in lower dust retaining capability of the
surface, etc. (Tervahattu et al., 2006; Raisanen et al., 2005;
Kupiainen et al., 2003, 2005; Kupiainen and Tervahattu, 2004).
The impact of different road pavement aggregates in the genera-
tion of PM10 was deeply investigated by previous studies: Gehrig
et al., 2010 studied the effect of Asphalt concrete and Porous
asphalt on PM10 emission finding lower emissions with the
porous pavement which retains deposited dust better than dense
pavement. Gustafsson et al., 2009 found that granite asphalt
concrete produces 70% more road wear emissions than quartzite
concrete asphalt. Tervahattu et al., 2006 found lower emissions
when mafic volcanic rock was used as asphalt concrete with
respect to standard granite rocks.
XRD results reveal a mineralogy which in all three groups of
samples is dominated by quartz, alkali feldspars, carbonate and
phyllosilicates (clay minerals). Minor phases identified in some
samples include iron oxides (hematite, magnetite), Na-carbonate,
talc, and FeMg amphibole. Quartz is the most common mineral in
all the Zürich samples, as well as in most of those analyzed from
Girona and Barcelona. This is likely to be a road pavement-related
signature, given the abundance of granite stones in all pavements
of sampling roads. The exceptions to this are two sites in Girona
(c/Barcelona and Plaça Espanya) and one site in Barcelona Harbor
(Dressanes), where the content of carbonate minerals (calcite and
dolomite) exceeds that of quartz. Apart from these three
 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787 6781

Table 1
Average loading of road dust <10 mm at each location, short description and traffic intensities. SD: standard deviation.

City Code Location Remarks (surface type) Vehicles day
1 Vehicles speed Loading SD
(Fig. 1) (HDV) (km h
1) (mg m
2)
Zürich 8 Kaserme Urban background 0 e 0.8 0.3
(old asphalt concrete)
4 Eichbühlstrasse Residential <1000 (na) 50 0.9 0.8
6 Duttweilerstrasse City exit, new pavement (Nov. 2007) 13000 (7%) 50 0.2 0.1
Stone mastic asphalt (11PmB)
1 Weststrasse Street canyon (old asphalt concrete AB12) 21000 (7%) 50 1.3 1.3
2 Schimmelstrasse Crossing (Old surface, stone mastic 26000 (7%) 50 0.6 na 0.4
asphalt or stone asphalt.
3 Hardplatz Crossing (Stone mastic asphalt, 2006) 31000 (7%) 50 0.6 0.4
5 Pfingstweidstrasse City exit (Asphalt concrete AB16) 40000 (9%) 60 0.4 0.4
7 Milchbuck Tunnel Tunnel 30000 (4%) 50 0.7 0.4

Barcelona 1 Dressanes Roundabout 40000 (na) 50 13.4 4.9

6 Maciá Roundabout 100000 (na) 50 5.8 1.8
4 Cerdá Roundabout/harbor 40000 (na) 50 23.1 3
8 C31 Roadway City exit 22000 (na) 80 6 3.2
9 Rovira Tunnel Tunnel 23000 (na) 50 3.7 1.2
2 España Roundabout 120000 (na) 50 5.5 1.3
3 Diagonal City entrance 132000 (na) 50 5.4 2.5
5 Valencia Crossing 80000 (na) 50 13.2 2.1
7 Joan Carles Roundabout 80000 (na) 50 3.7 1.4

Girona 2 Baldiri Reixach Residential 2000 (na) 50 1.4 1

3 Pompeu Fabra Construction site na 50 48.7 12.8
4 Reggio Emilia e 40000 (na) 50 1.4 0.1
5 Sant Narcis Stones 12500 (na) 50 3.2 0.2
7 Pl. Espanya Next to unpaved area 40000 (na) 50 1.3 0.4
6 c/Barcelona e 40000 (na) 50 4.4 2.1
1 Santa Eugenia Next to unpaved area 25000 (na) 50 7.1 0.5

Barcelona II 10 Dalt S.1 Ring road 170000 (na) 80 12.8 6.9

11 Dalt S.4 Ring road 170000 (na) 80 73.7 31.2
12 Litoral 24 Ring road 120000 (na) 80 23.7 10
13 Litoral 21 Ring road 120000 (na) 80 23.4 9.9
14 B10 pk 15 Ring road 120000 (na) 80 25.6 2.5
15 B10 s20 Ring road 120000 (na) 80 36.8 15
16 Meridiana-Dublin City entrance-Kerbside works 100000 (na) 50 80.2 30.9
17 Port Harbor exit <1000 (na) 50 165.4 131
18 Meridiana-Palencia Main city entrance 100000 (na) 50 137.9 27.3
19 Provençal/Llull Construction site 6500 (na) 50 328.8 53.6
20 Selva de Mar 150 m from construction site 4000 (na) 50 471.3 114
21 Bac de Roda 300 m from construction site 4000 (na) 50 133.3 65.5
22 Selva de Mar II 400 m from construction site 4000 (na) 50 11.7 11.1
23 Gracia i Faria 480 m from construction site 13000 (na) 50 2.5 1.1
24 Selva de Mar III Central traffic lane 4000 (na) 50 5.1 1.1
25 Pl. Levant Roundabout 2000 (na) 50 4.1 1.5

exceptions, the combined content of calcite and dolomite form K-feldspar) comprise the third largest rock forming mineral
the second most common group of minerals after quartz. Calcite is group, with albite always being the more abundant of the two.
more common than dolomite, especially in Barcelona where Again, their presence is strongly related to road pavement eroded
dolomite content is always low. Alkali feldspars (both albite and particles (Tervahattu et al., 2006; Raisanen et al., 2005; Kupiainen

100%
Percentage of analyzed species

80%
Trace elements
K+Na+Mg+Cl+P+S
60% Ca
Al2O3
SiO2
40% Fe
NO3-
EC
20%
OC

0%
Barcelona Girona Zürich

Fig. 3. Average chemical composition of road dust <10 mm at the three cities studied (% of identified mass).
6782 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787

et al., 2003, 2005; Kupiainen and Tervahattu, 2004). The albite Table 2
content of the samples collected at construction sites is especially Relative concentrations of major and trace components in road dust <10 mm
samples at the three cities studied (only city center samples).
high, and may derive from dust produced from a number of
construction materials such as sand, aggregates or cutting of Zürich Barcelona Girona
natural stones. The phyllosilicate mineral assemblage detectable Mean SD Mean SD Mean SD
using XRD includes illite, muscovite, chlorite (clinochore), Road dust <10 mm 0.7 0.3 8.9 6.5 3.5 2.4
kaolinite, and palygorskite. Of these, illite (a KeFe bearing clay (mg m
2)
mineral) is the most frequently present, presumably representing
resuspended soil materials derived from the geological weath- %
OC 21.4 12.5 11.7 1.8 10.9 5.2
ering of felsic silicates (usually feldspar). The white mica
EC 7.2 3.7 3.0 1.5 4.6 3.4
muscovite is much less common than illite, but is clearly present SiO2 11.0 5.9 19.3 9.0 33.5 6.4
in most of the Barcelona samples, especially in that collected at Al2O3 2.8 1.6 8.0 3.7 13.6 3.3
the construction work site (where illite content is unusually low), Ca 8.1 3.7 13.2 4.8 20.6 9.1
again probably recording the anthropogenic use of building K 2.0 0.7 1.4 0.6 1.8 0.8
Na 0.6 0.5 0.5 0.1 0.7 0.2
materials. Finally Fe-oxides and talc might be locally related to Mg 0.8 0.4 1.2 0.5 1.8 1.0
brake wear and catalyst (only for talc, http://www.luzenac.com/ Fe 4.6 3.4 5.0 2.1 5.8 1.7
ceramics.htm). P <DL 0.1 0.1 0.2 0.0
Relative mean concentrations of major road dust components S 0.4 0.2 0.7 0.2 0.9 0.2
NO
4.6 3.3 0.3 0.3 0.3 xx
data for the three sites are summarized in Fig. 3. The most imme- 3
Cl
0.7 0.4 0.5 0.3 1.0 1.2
diately obvious differences between the sites are the high relative
abundance of OC þ EC and NO
3 , and the low amounts of crustal mg g
1
silicates at Zürich compared with Barcelona. These differences are Li 17 9 36 15 26 6
further investigated in Table 2 which shows also relative trace Sc <DL 3 3 4 3
element concentrations averaged for the three sites. Once again it is Ti 1488 561 2964 1207 2113 395
V 56 25 84 32 54 13
apparent from these data that the Barcelona samples are relatively Cr 330 221 229 105 188 87
enriched in crustal elements, notably Ti, Rb, Sr, Cs, and the Mn 614 308 654 242 473 121
lanthanide elements La and Ce. In contrast, Zürich PM is appre- Co 22 14 10 4 12 3
ciably more contaminated by anthropogenic metals. Averaged Ni 504 369 58 15 191 131
Cu 3547 2233 1332 705 1055 638
levels of Cu, Mo, Co, Zr, Ni, Sb, As, Nb, Zn and Cr are all over 40%
Zn 2183 997 1572 440 1760 705
higher in Zürich than in Barcelona. This metal enrichment is further Ga 15 8 12 5 10 2
demonstrated by Figure S2 which compares the data with the Ge 18 11 14 9 6 7
composition of the upper continental crust, normalizing each value As 19 11 12 4 11 1
to Al. The trace metals/metalloids that are most obviously enriched Se 7 10 4 2 8 3
Rb 37 17 65 28 55 15
with respect to the Upper Continental Crust are Cd, Sb, As, Mo, Sn, Sr 202 88 243 69 136 43
Ni, Pb, Cu, Zn, Ba. Of these, Sb, Mo, Sn, Ni, Cu and Zn are most Y 15 6 12 6 12 3
prominently enriched in Zürich, a distinctive signature attributed Zr 806 400 120 42 276 178
mainly to the influence of traffic contamination. Vanadium showed Nb 23 15 14 5 20 4
Mo 199 164 84 44 124 115
pretty constant concentrations except in Barcelona, where the site
Cd 10 5 3 1 2 1
closer to the harbor showed twice as much Vanadium. Interestingly Sn 342 289 233 140 155 106
the ratio Ce/La, typically 2 in crustal materials, showed an average Sb 324 288 196 103 64 43
value of 3.5 in Zürich. Cs <DL 4 2 2 2
Regardless of the city categories, sampling sites were grouped Ba 1509 437 1390 459 2159 1281
La 10 4 20 8 16 5
based on mean daily traffic volumes (Fig. 4). Three categories were Ce 35 15 45 21 39 11
selected, namely <15 kveh day
1, within 15ke40 kveh day
1 and Hf 39 20 4 1 12 8
>40 kveh day
1. While no patterns were observed for relative W 12 4 8 8 1 3
concentrations of road dust components, a clear increase of abso- Pb 247 98 248 100 128 36
lute loadings (mg m
2) was found for several components (OC, EC, Bi 21 23 9 5 5 4
Th 9 4 7 3 6 1
Fe, Cr, Mn, Cu, Zn, Mo, Sn, Sb, Cs, Ba, W, Pb and Bi), revealing the U 10 6 2 1 3 1
existence of some relationship between number of vehicles and
loadings of (deposited) specific pollutants below 10 mm. An increase
from the <15 kveh to 15e40 kveh day
1, therefore of a factor
around 2, revealed an increment of pollutant loads (mg m
2) by vehicles-road wear is one of the 3 major sources of road dust
a factor of 1.2e2.2. At highly trafficked sites (>40 kveh day
1) road particles. More research is however needed.
dust loadings were again increasing by a further factor of 2.6e10.1. Cu and Sb ambient concentrations and their ratio have already
Conversely, loadings of other components such as crustal species been shown in the literature to be useful chemical tracers for brake
(Si, Al, Ca, Mg, Ti etc.), sea salt (Na, Cl
) and other trace elements wear related emissions. Brake pad compositions normally show
(V, Ni, Cd, As, etc.) not uniquely generated by road traffic were values for Cu/Sb in the range of 9e18 (Adachi and Tainosho, 2004;
varying independently from the number of vehicles circulating. Iijima et al., 2007) although it can be below 2 (von Uexkull et al.,
Total loads of particles <10 mm showed average values of 2005; McKenzie et al., 2009) depending on the manufacturer.
1.3  1.1 mg m
2 in roads with <15 kveh, 5.2  6.8 mg m
2 at roads When referring to ambient concentrations of Cu and Sb in the PM10
with 15e40 kveh and 6.7  3.7 mg m
2 at roads with fraction the ratio Cu/Sb lies between 4 (Zereini et al., 2005) to more
>40 kveh day
1. This might be influenced by the fact that most of common values of 7e9 in most urban sites (Weckwerth, 2001;
the very trafficked roads were in Barcelona, however a general link Sternbeck et al., 2002; Schauer et al., 2006; Perez et al., 2008;
between number of vehicles and particles loads cannot be dis- Amato et al., 2009b; Gietl et al., 2010; Pey et al., 2010; Fujiwara
carded, since as demonstrated in the source apportionment section, et al., 2011). In this study, only in Barcelona we found a constant
 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787 6783

Fig. 4. Average loadings of road dust components at road categories with increasing traffic volumes.

Cu/Sb ratio (6.8  0.9) among samples, while in Zürich and Girona, 10% in Girona and Barcelona II batches. Tire wear contributes
the ratio was varying considerably, being the averages values generally less than 40% at all cities. Interestingly high contributions
13.5  6.1 and 17.0  8.9 respectively. Nevertheless, as shown in from tire wear were found in Barcelona II locations, with a higher
Fig. 5, a relationship was found between the amount of Cu and Sb in share of HDV.
road dust <10 mm (ng m
2) and the atmospheric concentration of
Cu and Sb from literature studies (Hueglin et al., 2005; Perez et al.,
2008) at urban background sites. This finding may be explained Concentrations in PM10 in ambient air
either because in the cities studied Cu and Sb are mostly emitted to
90
atmosphere by traffic resuspension and the emissions depend on
road dust loads, or because road dust build-up is controlled mostly
80 Zürich
by PM deposition. With this in mind a source apportionment study
70 Barcelona
was performed on the levels and chemical characterization of road 60 Girona
ng m-3

dust <10 mm measured at Barcelona, Zürich and Girona city centers 50

in order to further understand the main causes of road dust build- 40

up and how these sources contribute to different urban regions. 30

A Positive Matrix Factorization was performed on this 20
assembled dataset including loadings from the three urban 10
environments. Four factors were identified: namely Road wear/ 0
Mineral (traced by typical crustal species: Al, Ca, Fe and V, Cu Sb
probably related to the bitumen of asphalt), Vehicular Exhaust
(EC and OC,), Brake wear (Fe, Cu. Zn, Cr, Sn and Sb) and Tire Wear
(OC, S and Zn) (Fig. 6). The brake wear factor looks convincing but Loadings in road dust < 10 µm
the inclusion of significant associations with antimony and 14000
barium in the tire wear factor suggests some mixing with the 12000
brake wear factor.
10000
Source contributions are depicted for any single sample in Fig. 7,
ng m-2

where also the variability within the same city can be noticed. Road 8000
wear/Mineral contribution, accounting for the wear of road surface
6000
and the deposition of urban background mineral dust (urban works
mostly) is the main source of road dust in Barcelona and Girona 4000

(60% in average, and never less than 30%) while it represents less 2000
than 30% in average Zürich (varying from 15 to 60%) (Fig.7). In the
0
second sample batch of Barcelona, road/wear contributions are
Cu Sb
even higher than in the city center due to the presence of uncov-
ered trucks transporting dusty materials. Motor exhaust particles
Fig. 5. Top: Levels of Cu and Sb measured in ambient air (PM10 for Zürich, Bukowiecki
contribute similarly in Girona and Zürich (up to 60%), while they do et al., 2009; PM10 for Barcelona, Perez et al., 2008; PM2.5 for Girona, own unpublished
not exceed 20% of road dust loadings in Barcelona. Brake wear data). Bottom: road dust <10 mm samples in the city centers of Zürich, Barcelona and
contributes in average w15% in Zürich and Barcelona, but less than Girona.
6784 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787

Conc. (g/g) Explained variation In both Barcelona and Zürich the relationship between
1 1
deposited loadings of a given pollutant (mg m
2) and the corre-
Tire wear 0.8 sponding emission factors (PM10) estimated by other studies
0.1

0.6
(Bukowiecki et al., 2009; Amato et al., 2010) was explored. As
0.01 shown in Fig. 8, the Emission Factors available from literature for
0.4
PM10, Fe, Cu, Sn and Sb are plotted against the mean loadings of
0.001
0.2 corresponding species as deposited material (x axis) found in this
0.0001 0 study. In both cases (Barcelona and Zürich) for PM10, Fe, Cu, Sn
Al Ca Na Fe S V Cr Ni Cu Zn Sn Sb Ba OC EC and Sb a relationship (potential curve) was found. This relation-
Conc. (g/g) Explained variation
ship confirms first that the relative concentrations found in road
1 1 dust (<10 mm) are in agreement with the relative concentrations
Brake wear found in bulk materials emitted by traffic-induced resuspension.
0.8
0.1 Furthermore, the two curves are similar, so that if combined, the
0.6 potential curve obtained (EF ¼ 45.9 RD0.81) might be used to
0.01
0.4 estimate emission factors from known amount of particles <10 mm
0.001 deposited on the road. For example in the case of Girona, we can
0.2
estimate emission rates of 35 mgPM10, 3448 mgFe, 133 mgCu,
0.0001 0
14 mgSb and 28 mgSn emitted by a single vehicle of the average
Al Ca Na Fe S V Cr Ni Cu Zn Sn Sb Ba OC EC
local fleet per kilometer traveled. Since no reference emission
Conc. (g/g) Explained variation factors values are available from literature, the values obtained in
1 1 the study must be taken only as rough estimates. For example,
Road wear / Mineral
0.8
they would change considerably if only the curve fitted for Bar-
0.1
celona was used. More investigation is needed in this sense, but it
0.6
0.01
is likely that the curve should be applied to cities with similar
0.4 climatic conditions.
0.001
0.2
Interestingly, this formula has the same form (y ¼ a xb) as
the EPA-AP-42 formula proposed to estimate emission factors from
0.0001 0
Al Ca Na Fe S V Cr Ni Cu Zn Sn Sb Ba OC EC
silt loading loadings. The EPA-AP-42 formula has been keenly crit-
icized by several authors for two main reasons: the poor mecha-
Conc. (g/g) Explained variation
nistic basis Venkatram (2000, 2001), and the incongruence
1 1
with the EFs experimentally determined locally (Zimmer et al.,
Motor exhaust 0.8 1992; Kantamaneni et al., 1996; Ashbaugh et al., 1996).
0.1

0.6 Venkatram (2000) finally concluded that AP-42 model is not likely
0.01 to provide adequate estimates of PM10 emissions from paved
0.4
roads, since it relies on an input variable, the silt loading, which
0.001
0.2 cannot be measured unambiguously. Another point of criticism is
0.0001 0 the assumption that emission depends only on silt load and weight
Al Ca Na Fe S V Cr Ni Cu Zn Sn Sb Ba OC EC of the vehicles. It has been shown that a number of other factors can
influence this emission rate (Nicholson, 1988; Nicholson and
Fig. 6. PMF source profiles of road dust particles in Barcelona, Zürich and Girona.

Zürich Barcelona
100 100
1 2 3 1 2 3
80 80

60 4 5 6 60 4 5 6

40 40

20 7 8 20 7 8

0 0

Tire Brake Road wear Motor Tire Brake Road wear Motor
wear wear /Mineral exhaust wear wear /Mineral exhaust

Girona Barcelona II
100 100 9 10
11 12
1 2 3
80 80 13 14
15 16
60 60
17 18
40 40 19 20
4 5 6 21 22
20 20 23 24
25
0 0

Tire Brake Road wear Motor Tire Brake Road wear Motor
wear wear /Mineral exhaust wear wear /Mineral exhaust

Fig. 7. Source contributions (in %) to road dust levels (<10 mm) registered in each sample of Zürich, Barcelona, Girona and Barcelona II datasets.
 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787 6785

1E+06

Bukowiecki et al., 2009; Amato et al., 2010

Observed EF (µg veh km )
1E+05 0.8192

-1
y = 52.949x

-1
1E+04

1E+03

0.7722
y = 41.281x
1E+02

1E+01 Barcelona
Zürich
1E+00
1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05

Deposited (<10µm) µg m-2

Fig. 8. Observed emission factors (EF) in Barcelona and Zürich against mean values of road dust <10 mm.

Branson, 1990). Particularly vehicle speed seems to play an The principal sources responsible for road dust build-up and
important role. their contributions to road dust levels were investigated by means
In the present case the novelty of our formula consists in the of a standard multivariate receptor model (PMF) commonly used
implementation of loading of sediments <10 mm, the same particle for the source apportionment of ambient air PM. Four main sources
size used to calculate emission factors in literature rather than silt of road dust <10 mm were found: namely Road wear/Mineral,
(<63 mm) loading. Even if the uncertainties from the non- Motor Exhaust, Brake wear and Tire Wear. We can conclude, with
mechanistic approach of AP-42 are not solved, a satisfactory the given caution due to uncertainty in receptor modeling, that the
agreement between observed and predicted emission factors was Road wear/Mineral is the dominating source in Spanish cities
found. More investigations are certainly needed in order to deter- (w60%), but represents only 30% of road dust loadings in Zürich
mine whether formulas validated by, or based on, experimental where contributions are more equally distributed among the four
methodologies should be applied for other locations with different main sources of road dust.
traffic densities and environmental conditions. Regardless of the city categories, an increase of some specific
road dust components (OC, EC, Fe, Cr, Mn, Cu, Zn, Mo, Sn, Sb, Cs, Ba,
4. Conclusions W, Pb and Bi) loads (mg m
2) by a factor of 1.2e2.2, was found
passing from streets with <15 kveh to 15e40 kveh day
1. At highly
Loadings of road dust <10 mm from the 8 sites sampled in Zürich trafficked sites (>40 kveh day
1) loadings were again increasing by
(Switzerland) range from 0.2 to 1.3 mg m
2, with an average of a further factor of 2.6e10.1. No clear patterns were observed for
0.7 mg m
2, making this site the least contaminated of the 3 under loadings of total particles <10 mm.
study. The minimum loadings in Girona (Spain) were as high as the Finally an agreement was found between the composition of
maximum in Zürich, with a range of 1.3e7.1 mg m
2 and an average sampled materials and the composition of PM10 material emitted
of 3.5  2.4 mg m
2. By far the most polluted site in terms of road by vehicles via resuspension (available from literature) in Zürich
dust <10 mm mass loading is Barcelona (Spain), where a range of and Barcelona (Bukowiecki et al., 2010; Amato et al., 2010). This
3.7e23.1 mg m
2 and an average of 8.9  6.5 mg m
2 were permitted to find a relationship, potentially able to calculate
recorded in the city center. Ring roads (high share of HDV), harbor emission factors from known amount of deposited pollutants in
and construction sites registered very high loadings, as expected. those cities/environment where no real-world EFs are available
X-ray diffraction of total sediments, although unable to fully char- from literature.
acterize samples, permitted to identify quartz, carbonate, alkali The results presented have important implications for
feldspars and phyllosilicates as main phases. Minor phases recog- scientific and policy perspective: firstly, the chemical analysis of
nized in some samples include iron oxides, Na-carbonate, talc, and the collected samples provides valid emission profiles useful for
FeMg amphibole. The albite content and white mica muscovite may airborne PM source apportionment studies. The Chemical Mass
derive from construction dust produced during the handling of Balance (CMB: Watson et al., 1984; Cheng and Hopke, 1986;
building materials. Hopke and Song, 1997) approach and recent applications of
The larger chemical differences between the 3 cities are the target factor analysis techniques have shown the importance of
relative abundance of OC þ EC and NO
3 , and the low amounts of characterizing local source profile of PM for a reliable estimate
crustal silicates at Zürich when compared with Barcelona. Averaged of the source contributions to atmospheric PM (Amato et al.,
levels of Cu, Mo, Co, Zr, Ni, Sb, As, Nb, Zn and Cr are all over 40% 2009a; Escrig et al., 2009). Secondly, the field observations
higher in Zürich than in Barcelona (in relative concentrations). This here reported are of primary interest for dispersion modeling,
metal enrichment is further demonstrated by the elemental ratios since they explore the spatial variation of the strength of
compared to composition of upper continental crust, normalizing different PM10 sources (resuspension and brake wear) by means
each value to Al. The highest enrichments were found in Zürich, of the loadings (mg m
2) of sediments below 10 mm and specific
with a distinctive signature attributed mainly to the influence of tracers such as Cu and Sb. These observations are needed for
traffic contamination. constructing new modules (functions for dispersion modeling)
6786 F. Amato et al. / Atmospheric Environment 45 (2011) 6777e6787
to describe spatial variability of Emission Factors for non-
exhaust sources of PM (see Omstedt et al., 2005 for temporal
variation). Moreover, the rough estimates of the characteristic
levels of road dust (mg m
2) in different cities can be used to
evaluate the effectiveness of street cleaning if coupled with data
on deposition fluxes (mg m
2 h
1). Finally, knowing the major
sources of road dust and their contributions is a key step in
selecting environmental policy measures to reduce PM emis-
sions by mitigating road dust resuspension.
Acknowledgments
This work was supported by research projects from the Spanish
Ministry of Environment (CALIOPE, 441/2006/3e12.1), the Spanish
Ministry of Sciences and Innovation (GRACCIE-CSD2007-00067,
DOASUR CGL2007-62505/CLI), two short-visit grants from INTROP
(Interdisciplinary Tropospheric Research) and one I3P fellowship
from the Spanish Council of Research (CSIC).
Appendix. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.atmosenv.2011.06.003.
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