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Atmospheric Environment 36 (2002) 949961
Chemical characterization and source identification/
apportionment of fine and coarse air particles
in Thessaloniki, Greece
E. Manoli, D. Voutsa, C. Samara*
Environmental Pollution Control Laboratory, Department of Chemistry, Aristotle University of Thessaloniki, 540 06 Thessaloniki, Greece
Received 23 April 2001; received in revised form 10 September 2001; accepted 17 September 2001
Abstract
The distribution of air particulate mass and selected particle components (trace elements and polycyclic aromatic
hydrocarbons (PAHs)) in the fine and the coarse size fractions was investigated at a traffic-impacted urban site in
Thessaloniki, Greece. 7676% on average of the total ambient aerosol mass was distributed in the fine size fraction.
Fine-sized trace elemental fractions ranged between 51% for Fe and 95% for Zn, while those of PAHs were between
95% and 99%. A significant seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger
fine fractions in winter. Similar seasonal trend was exhibited by PAHs, whereas larger fine fractions in summer were
shown by trace elements. The compositional signatures of fine and coarse particle fractions were compared to that of
local paved-road dust. A strong correlation was found between coarse particles and road dust suggesting strong
contribution of resuspended road dust to the coarse particles. A multivariate receptor model (multiple regression on
absolute principal component scores) was applied on separate fine and coarse aerosol data for source identification andapportionment. Results demonstrated that the largest contribution to fine-sized aerosol is traffic (38%) followed by
road dust (28%), while road dust clearly dominated the coarse size fraction (57%). r 2002 Elsevier Science Ltd. All
rights reserved.
Keywords: Air particles; Trace elements; Polycyclic aromatic hydrocarbons; Receptor models; Principal component analysis
1. Introduction
Recent concern about the health effects of air
pollution has focused on particulate matter (PM) andseveral epidemiological studies have indicated a strong
link between elevated particle concentrations and
increased mortality and morbidity (Dockery and Pope,
1994). Despite the drastic reduction of urban particulate
pollution in cities resulted from the improvement of coal
usage and the shift toward other fossil fuels (oil or
natural gas) for domestic heating, the densification of
the urban net combined with population growth and
increasing importance of traffic have contributed to
reinforce urban particulate pollution. Furthermore,
particles produced by cars are much smaller than coal
particles and found in the breathable size fraction.
A bimodal distribution of ambient aerosol has beenreported for many urban sites (Aceves and Grimalt,
1993; Lin et al., 1999; Lioy and Daisey, 1987). The
coarse fraction is mainly due to crustal material, paved-
road dust, non-catalyst equipped gasoline engines and
background sea salts. The fine fraction is a mixture of
primary and secondary aerosol emitted from anthro-
pogenic rather than natural sources or formed by
vapour nucleation/condensation mechanisms (Kleeman
and Cass, 1998; Hildemann et al., 1991). Current
research is focused on fine particles (PM2.5) because
they may be transported over long distances, penetrate
deep into the lungs and are also enriched with toxicants.
*Corresponding author. Fax: +30-31-997747.
E-mail address: [email protected] (C. Samara).
1352-2310/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 2 - 2 3 1 0 ( 0 1 ) 0 0 4 8 6 - 1
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Since strategies to improve ambient air quality in
large urban centres typically involve the reduction of
emissions from primary sources, it is useful to be able to
observe the separate contributions that different sources
make to the ambient particle size distribution and
chemical composition. In recent years, receptor models
have been proved as being important tools for separatelyvisualizing source contributions to particulate air quality
(Lioy and Daisey, 1987; Ehrman et al., 1992; Thurston
and Spengler, 1985; Samara et al., 1994a, b). However,
relatively limited research has been done on the
identification and the apportionment of size-related
aerosol sources (Ehrman et al., 1992; Thurston and
Spengler, 1985; Kleeman and Cass, 1998; Miranda et al.,
1996; Swietlicki et al., 1996).
The objectives of this paper were: (a) to investigate the
distribution of particle mass and particle components,
such as trace elements and polycyclic aromatic hydro-
carbons (PAHs), in the fine and the coarse size range inan urban location, and (b) to use a suite of aerosol data
for source identification and apportionment. The
research was conducted at a traffic-affected site of the
city of Thessaloniki in northern Greece, in the frame-
work of a long-term research aiming at the investigation
of local air particles with respect to size distribution,
chemical composition and sources of emission (Viras
et al., 1991; Samara et al., 1990, 1994a,b, 1995;
Misaelides et al., 1993; Tsitouridou and Samara, 1993;
Kouimtzis et al., 1995; Samara and Tsitouridou, 2000).
2. Experimental
2.1. Site description
Thessaloniki (401620E, 221950N) is one of the most
densely populated cities in Greece and in Europe (16,000
inhabitants km2). It is a coastal city surrounded by
several stable residential communities while an extended
industrial zone is located north-westerly. Oil refining,
petrochemical, fertilizer and cement production, non-
ferrous metal smelting, iron and steel manufacturing,
truck and auto painting, metal recovery facilities,
electrolytic MnO2
production, anodized Al, scrap metalincineration, tire production and lubricating oil recovery
are the main industrial activities in the area.
The climate of Thessaloniki is temperate strongly
influenced by the sea breeze. Mean monthly values of
relative humidity range between 47% and 80%, while
those of temperature between 5.51C (in January) and
281C (in August). Prevailing wind directions are N/NW
(B25%), S/SW (B30%) and calms (B20%).
2.2. Sampling and analysis
Aerosol sampling took place in a residential/commer-
cial area, at a site located aside one of the citys busiest
roadways comprising six lanes (three each way). The
average traffic working-day rate at this site is 2800
vehicles/day. Although there is a continuing change
in the size and composition of motor fleet, at the time
of the study buses accounted for about 10% of the
overall fleet and taxis (diesel engined) for another 10%.
The rest were gasoline engined passenger cars, about40% fitted with catalytic converters. The sampler was
situated on the roof of an atmospheric pollution
monitoring station (B3 m a.g.l.) located 5 m aside the
closest lane.
Fine (o3mm) and coarse (310 mm) aerosol samples
were collected on 45 working days within the period
June 1994May 1995. A high-volume cascade impactor
(Sierra Instruments) providing a 50% cut-off point of
3.0 mm at 40 CFM was used for this purpose. Fine and
coarse particles were collected on glass fibre filters
(1000 1500 sheets and 500 700 slotted sheets, respec-
tively). All samplings had a 24 h duration. Loaded andunloaded filters were dried in a darkened desiccator for
24 h before weighing. Loaded filters were stored in the
dark, in aluminium foils, at 201C until extraction and
analysis could be completed.
Half of each loaded filter was ultrasonically treated
with a mixture of concentrated HNO3 and HCl for trace
element extraction (Samara et al., 1990). Extracts were
subsequently submitted to flameless (for Cr, Cd, Cu,
Mn, Pb, Zn, Fe, Ni, V) or hydride generation AAS (for
As), according to standard analytical procedures. The
analytical precision of all elemental species was better
than 10%.
The other half of the filter was used for PAH analysis.
The extraction procedure and the method of determina-
tion are described in detail elsewhere (Samara et al.,
1995; Papageorgopoulou et al., 1999). Briefly, filter
samples were ultrasonically extracted with acetonitrile
under recovery rates in the range 87102%. No further
clean-up was performed. Concentrated extracts were
analyzed by means of reversed-phase HPLC using
fluorescence detection. Separation was performed on a
5 mm Hypersil Green PAH column (100 4.5 mm2) with
corresponding guard cartridge. The mobile phase was a
CH3CNH2O gradient comprising 50% CH3CN over
5 min, 50100% CH3CN between 5 and 20min and100% CH3CN for 10 min. Five pairs of excitation and
emission wavelengths were used for detection. The
system was calibrated with 16 PAHs, 15 compounds
(acenaphthylene was omitted since it is only weakly
fluorescent) specified in the EPA Method 610 (US EPA,
1977), plus benzo[e] pyrene which is frequently used as a
reference PAH. The precision of all identified species
was better than 10% for peak height.
Road dust was collected from the road side near the
aerosol sampler. The fractiono2 mm was used for trace
element and PAH analysis employing the same methods
as for filter samples.
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2.3. Data analysis techniques
Statistical analysis of data (analysis of variance,
correlation analysis, absolute principal component
analysis (PCA)) was performed using the SPSS statis-
tical software (SPSS Inc., 1998).
3. Results and discussion
3.1. Concentrations of fine and coarse-sized species
Tables 1 and 2 show a breakdown of the concentra-
tions of PM and individual particle components found
in each size fraction, while the seasonal variability of
concentrations is given in Table 3.
As shown, the total (fine+coarse) particle concentra-
tions measured were towards the highest values
reported for urban PM10 (Turnbull and Harrison,
2000; Ruellan and Cachier, 2001; Harrison and Jones,
1995; Balachandran et al., 2000; Kao and Friedlander,1995). Historically, Thessaloniki has been encountered
serious air-quality problems with air particles, with TSP
concentrations exceeding by far the annual limit of
150 mg m3. Although a 30% reduction has been
obtained during the last decade, current TSP levels are
still high. According to the Directive 1999/30/EC, from
1 January 2001 Member States are obliged to measure
Table 1
Particle mass (mg m3) and elemental concentrations (ng m3) in the fine and coarse fraction
Species Fine (N 45) Coarse (N 45) ra
Mean Median Min Max Mean Median Min Max
PM 97 102 15 174 30 32 6 62 0.699**
As 1.5 1.5 0.4 2.8 0.61 0.52 0.33 1.12 0.366*
Cr 4.8 3.6 1.2 18.8 2.9 1.9 0.4 21 0.184
Cd 0.87 0.70 0.15 3.90 0.11 0.10 0.05 0.40 0.429*
Cu 168 142 45 542 90 92 39 160 0.256
Mn 23 21 8 42 24 15 1 110 0.260
Pb 127 108 32 386 29 30 7 58 0.104
Zn 521 441 227 1631 25 24 4 56 0.167
Fe 297 300 80 529 291 306 52 568 0.431*
Ni 17 15 3.2 42 6.1 5.0 1.9 13 0.497*
V 41 27 3.0 116 6.9 5.2 1.3 27 0.024
aSpearman correlation coefficient between fine and coarse concentrations.
*Correlation significant at the 0.01 level.
**Correlation significant at the 0.05 level).
Table 2
PAH concentrations (ng m3) in the fine and coarse fraction
Species Fine (N 45) Coarse (N 45) ra
Mean Median Min Max Mean Median Min Max
Ph 1.81 1.49 0.46 7.54 0.08 0.06 0.01 0.24 0.376*
An 0.30 0.24 0.04 1.17 0.01 0.01 0.05 0.06 0.561**
Fl 6.15 5.02 1.00 17.24 0.12 0.10 0.02 0.27 0.574**Py 10.87 7.98 0.99 48.04 0.18 0.17 0.02 0.51 0.634**
B[a]An 1.85 1.41 0.25 5.97 0.02 0.01 0.05 0.08 0.748**
Chry 3.12 2.43 0.45 15.31 0.05 0.04 0.01 0.27 0.722**
B[e]Py 9.67 5.56 1.79 74.00 0.17 0.13 0.02 1.14 0.664**
B[b]Fl 2.77 2.40 0.53 8.96 0.04 0.03 0.01 0.14 0.696**
B[k]Fl 1.28 1.02 0.18 5.00 0.02 0.01 0.01 0.08 0.692**
B[a]Py 2.91 1.88 0.35 20.61 0.03 0.02 0.01 0.27 0.720**
dB[a;h] !An 0.67 0.47 0.10 3.82 0.01 0.01 0.05 0.04 0.675**B[ghi]Pe 6.58 5.11 1.23 26.00 0.10 0.08 0.01 0.36 0.734**
I[1,2,3-cd]Py 2.53 2.10 0.50 9.66 0.04 0.03 0.01 0.18 0.768**
aSpearman correlation coefficient between fine and coarse concentrations.
*Correlation significant at the 0.05 level.
**Correlation significant at the 0.01 level).
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ambient PM10 and PM2.5 concentrations and prepare
action plans for their reduction. A strict PM10 standard
(40 mg m3 annual average) has to be met by the year
2005 (EC, 1999), while a lower annual PM2.5 limit has
been recommended by the European Committee for
Standardization (20 mg m3, to be met by the year 2005,
CEN, 1997).
Trace elements and PAHs were found at concentra-
tions broadly consistent with those reported for various
urban European locations (Lee et al., 1994; Halsall et al.,
1994; Menichini et al., 1999). Mean Pb was below the
annual EC limit (500 ng m3), however, B[a]Py exceeded
the current standard set in Italy (1 ng m3, Valerio et al.,
1996). The profile of PAHs in fine and coarse aerosol has
been previously investigated by means of diagnostic
ratios and an overwhelming contribution of traffic
emissions was suggested (Samara et al., 1995).
The significant correlation found between fine and
coarse particle mass concentrations (Tables 1 and 2)suggests similar emission and dispersion processes for
the two modes. Significant, however, low correlation has
been reported for other sites (Burton et al., 1996). Fine
and coarse PAH concentrations were also strongly
correlated, particularly those of the heavier species,
underlying similar PAH sources in the two modes.
Moderate correlation was found between fine and coarse
Ni, Fe, Cd and As.
The mass concentrations of fine and coarse particle
fractions did not show significant seasonal variation
(Table 3). On the contrary, trace elements exhibited
variable seasonal trend. Concentrations of fine Cd, Cu,
Mn, Zn, Fe and V were significantly higher in summer
than in winter, whereas from the coarse elements only
Zn and Fe showed significant seasonal dependence.
When the mass proportion (ng mg1 aerosol) is con-
sidered, significant enrichment of fine particles with Cd,
Cu, Mn, Pb, Zn, Fe, Ni and V during summer is derived,
while coarse particles are also enriched in summer with
Zn and Fe. It could therefore be suggested that these
trace elements are preferably emitted from sources of the
warm period of the year. Concentrations of PAHs
bound to both fine and coarse particles showed a
significant seasonal trend with higher values during the
cold period. The reasons for that may be seasonal (as
their decay in the atmosphere will be slowest in the
winter months and also semi-volatile compounds will be
relatively enriched in particles due to lower temperatures
and high particle concentrations) and/or source-related
(due to the greater contribution of space heating and
road traffic in winter). On the contrary, the enrichmentof particles with PAHs was similar throughout the year.
Enrichment factors (EF) of trace elements in the fine
and coarse particle fraction relative to the earths crust
were calculated to indicate the extent of contribution of
sources other than natural crust to the ambient
elemental levels. The EF of an element E in an aerosol
sample is defined as
EF E atm=R atm
E crust=R crust;
where R is a reference element. There is no widely
accepted rule for the choice of the reference element; Si,
Table 3
Seasonal variability of particle mass and component concentrations
Species Fine Coarse
Colda
(N 34)
Warmb
(N 11)
Seasonal
variationcColda
(N 34)
Warmb
(N 11)
Seasonal
variationc
As (ngm3) 1.5 1.4 F 0.59 0.47 F
Cr (ngm3) 4.5 5.9 F 3.2 1.9 F
Cd (ngm3) 0.71 1.3 ** 0.12 0.10 F
Cu (ngm3) 135 270 ** 85 105 F
Mn (ngm3) 21 29 ** 27 14 F
Pb (ngm3) 122 141 F 29 29 F
Zn (ngm3) 408 872 ** 21 38 **
Fe (ng m3) 262 409 ** 263 377 *
Ni (ngm3) 15 21 F 6.4 5.2 F
V (ng m3) 35 60 * 7.0 6.7 F
SPAH (ng m3) 60 20 ** 0.97 0.51 *
PM (mg m3) 101 82 F 30 31 F
a
15 October 15 April.b15 April 15 October.c Insignificant at the 0.05 level.
*Significant at the 0.05 level.
**Significant at the 0.01 level.
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Al and Fe are usually used for this purpose. In this
study, Fe was used as reference, while the composition
of the earths crust was taken from Mason and Moore
(1982).
Results given in Fig. 1 show that Pb and Zn are the
most enriched elements in the fine size range followed by
Cd, Cu and As. For these elements non-crustal sourcesmay be suggested. Nevertheless, enrichment of crustal
components in fine particles can also occur as a result of
their transport to some distance before being removed
from the atmosphere by deposition processes (Kao and
Friedlander, 1995). Pb and Cu were the most enriched
elements in the coarse size fraction. On the other hand,
Mn and Cr showed low EF in both fractions thus
suggesting that crustal sources predominate in both size
ranges. Emissions from crustal sources are mostly in the
coarse particle size range, but 1130% of the PM10crustal mass has been reported as being in the fine
fraction (Kao and Friedlander, 1995). All elements, withimportant non-crustal sources (As, Cd, Cu, Pb, Zn, Ni,
V), exhibited lower EF values in the coarse mode. Lower
EF values with increasing particle size have been
reported for Pb, Zn, Ni and Cd (Bayens and Dedeur-
waerder, 1991; Santamaria et al., 1990; Chan et al.,
1997). On the other hand, Eleftheriadis and Colbeck,
1993, found increasing EFs with size for coarse V, Cu
and Cr with highest enrichment at around 10 mm and at
the very large sizes.
3.2. Distribution in the fine and coarse modes
The distribution of total particle mass and aerosol
components in the fine size range is presented in Fig. 2
for the cold and the warm time period. Fine particles
accounted for 7676% of the total PM, consistently to
reported values (5090%, Chan et al., 1997; Burton
et al., 1996; Ruellan and Cachier, 2001; Kao and
Friedlander, 1995). The fine particle fraction during
the cold period was slightly, yet significantly at the 0.05
level, higher than the corresponding summer fraction.
Similar seasonal trend was also observed in other works
(Chow et al., 1994; Harrison et al., 1997). Severalreasons could be responsible for that: higher strength of
fine particle emission sources (e.g. oil combustion for
heating and/or limitation of coarse particle resuspension
by wet precipitations during winter), aerosol dynamics
0
25
50
75
100
PM As Cr Cd C
uM
nPb Zn Fe Ni V Ph An Fl Py
B[]A
nCh
ry
B[e]Py
B[b]
Fl
B[k]F
l
B[]P
y
dB[
,h]A
n
B[gh
i]Pe
I[1,2,
3-cd
]Py
FIN
EFR
AC T
IO N
(% )
COLD WARM
Fig. 2. Distribution of particle mass and particle components in the fine size fraction.
0.1
1
10
100
1000
10000
Asfine
Asco
arse
Crfine
Crco
arse
Cufine
Cuco
arse
Cdfine
Cdco
arse
Pbfine
Pbco
arse
Mn
fine
Mn
coar
se
Znfine
Znco
arse
Vfin
e
Vco
arse
Nifine
Nico
arse
ENRICHMENTFACTOR
Fig. 1. EF (range and geometric mean) of fine and coarse-sized elements.
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(e.g. particle growth, dry and wet deposition) that
favour particle growth during summer, transfer of soil
dust with winds, etc. Lin et al. (1999) observed that the
distribution of ambient particles in Chicago between the
fine and the coarse mode was strongly dependent upon
the wind speed: low-speed winds raised the fine particle
fraction, whereas high-speed winds raised the coarseparticle fraction. Harrison et al. (1997) also reported
reduction of PM2.5 by increasing wind speed as a
dilution effect.
All elements which may be considered originating from
anthropogenic sources such as automotive traffic, oil
combustion or industrial processes (Pb, As, V, Ni, Zn,
Cd) exhibited a predominant occurrence in the fine
particle fraction (7095%). On the other hand, elements
such as Fe and Mn, which are also originating from
natural sources (soil dust) were almost equally distributed
in the two fractions. These findings are in general terms
consistent with the majority of the reported data (Chanet al., 1997; Santamaria et al., 1990; Lin et al., 1999; Rizio
et al., 1999; Harrison and Jones, 1995; Balachandran
et al., 2000). Nevertheless, different distributional data
have also been reported, as for example for Arnhem
aerosol, where the PM2.5 fractions of Zn and Cu
accounted only 25% and 10%, respectively, of the
corresponding PM10 fractions (Janssen et al., 1997),
and for aerosol in Long Beach, where the fine fraction of
Zn was found to be only 13% (Chow et al., 1994). A
seasonal effect significant at the 0.05 level was observed
on the distribution of Cd, Mn, and Ni, however, with
larger fine fractions in summer, contrarily to that
observed for particle mass. This is inconsistent with the
drift of the mass median diameters of trace elements (Ni,
Cu, Mn, Fe) to higher values in summer, which was
reported by Lyons et al. (1993) for Los Angeles.
Particle-bound PAHs were predominantly (9699%)
found in the fine size range despite the bimodal
distribution of particles. The proportion of PAHs in
fine particles was about one order of magnitude higher
than in coarse particles. The association of PAHs with
submicron ambient particles has been well documented
and attributed to their emission from combustion
processes (Cecinato et al., 1999; Poster et al., 1995;
Venkataraman and Friedlander, 1994; Aceves andGrimalt, 1993; Baek et al., 1991). Although no major
differences between low- and high-molecular weight
homologues were observed, a relative increase of the
lighter PAHs in the coarse size fraction is apparent and
might be attributed to differences in their sources, e.g. to
contributions from street dust which is dominated by
Ph, Fl and Py (Aceves and Grimalt, 1993) or to their
gas-particle partitioning behaviour (Venkataraman and
Friedlander, 1994).
The distribution of PAHs between the fine and the
coarse size fractions showed similar seasonal trend with
PM. In the cold period, the fine fraction of all PAH
species ranged between 96.1% and 98.4%, whereas in
the warm period it decreased slightly in the range 92.2
97.8%. This decrease was greater for the lower
molecular weight PAHs probably due to repartition
from the vapour phase onto larger particles under
certain conditions. Similar seasonal effect on the size
distribution of ambient PAHs has also been reported byother investigators (Aceves and Grimalt, 1993; Venka-
taraman and Friedlander, 1994; Baek et al., 1991).
Venkataraman and Friedlander (1994) observed that,
among the 5-ring and larger PAH species, B[a]Py
exhibited the strongest seasonal variability. The authors
attributed this variability to its greater reactivity in
comparison to the other non-volatile PAHs, that may
lead to a faster loss from the fine particle fraction due to
reactive decay in summer. In our study, the differences
between the winter and summer distributions for all
non-volatile PAHs were very low (0.21.1%), however,
the highest values were observed for the reactive B[a]Pyand dB[a;h]An.
3.3. Particle vs. road dust composition
Road dust has been reported as being important
contributor to airborne PM (Rogge et al., 1993; Ruellan
and Cachier, 2001). Resuspended by wind and vehicle-
induced turbulences, road dust particles from multiple
sources (automobile exhausts, lubricating oil residues,
tire and brake lining wear, street surface weathering, leaf
detritus, garden soil, etc.) are injected into the atmo-
sphere and redeposited. The chemical composition of
road dust, including trace metals and PAHs, has been
reported by several investigators (Hildemann et al.,
1991; Rogge et al., 1993).
The compositional signature of local road dust is
presented in Fig. 3 in comparison to the average
compositional signatures of fine and coarse particles.
All signatures were significantly correlated between each
other, however, the signature of road dust appeared to
be more strongly correlated to coarse particles
(r 0:568) than to fine particles (r 0:486). Thissuggests stronger contribution of road dust resuspension
to the coarse particle fraction.
3.4. Source identification and apportionment
Most source identification/apportionment applica-
tions have been based on inorganic aerosol components,
primarily trace elements often combined with ionic
components and/or gaseous pollutants (Kao and Fried-
lander, 1995; Lioy and Daisey, 1987; Ehrman et al.,
1992; Miranda et al., 1996; Swietlicki et al., 1996). The
potential use of PAHs as tracers of different combustion
sources has been explored by several investigators (Li
and Kamens, 1993; Lioy and Daisey, 1987). Three major
disadvantages make this use questionable: (a) different
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source categories have been found to provide similar or
overlapping fingerprints; (b) certain PAHs (e.g. B[a]An
and B[a]Py) have a relatively short atmospheric half-life
under photochemical smog conditions (Lioy and Daisey,
1987; Halsall et al., 1994; Schauer et al., 1996); (c) the
temperature-controlled vapour-particle partitioning of
the lower molecular weight PAHs (Ph, Fl, Py) can
probably affect PCA. (Harrison et al., 1996; Simcik et al.,
1999).
In the present study, source identification and
apportionment was performed on two separate data
sets combining trace elements and particle-bound PAHs.The model used consisted of first determining the
number and identity of sources using PCA with Varimax
rotation. Source contributions were calculated next by
using backward stepwise multiple regression of particle
mass concentration on the absolute principal component
scores (APCS) according to the equation:
Y r XP
j1
kiAPCSi;
where Y is the particle mass concentration, Ki is the ith
regression coefficient, p is the number of sources and r is
a constant representing the contribution from non-
specified sources. A detailed description of the modelling
approach can be found elsewhere (Thurston and
Spengler, 1985).
Tables 4 and 5 display the rotated PC loadings for the
fine and coarse aerosol fractions. Four PCs were
obtained with eigenvalues >1 summing almost 85% of
the total variance in the fine particle data set. The first
PC presented high loadings for the heavier PAHs (Chry
up to I[1,2,3-cd]Py) and for Pb, thus it was interpreted as
representing vehicle emissions (Harrison et al., 1996;
Simcik et al., 1999). The second PC was highly loadedon Ph, Fl, Py and B[a] An while showing moderate
loadings for benzo[b; k] fluoranthenes and I[1,2,3-cd]Py.Most of these PAHs have been reported as predominat-
ing in diesel particles (Harrison et al., 1996; Li and
Kamens, 1993). Therefore, PC2 was selected to represent
the diesel emission signal. The third PC was highly
loaded on Zn, Cu, Cd, Mn, Ni, Fe, Mn and Cr and was
interpreted as road dust. High loadings on Fe, Mn and
Cr reflect the bulk matrix of road dust which is soil,
while the correlation of the other metals indicate some
other sources as road dust, such as tire wear (source of
Zn), brakedrum abrasion (source of Fe), vehicular
Fig. 3. Compositional signatures of fine and coarse atmospheric particles and paved-road dust.
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Table 4
Rotated principal component matrix for fine aerosol (Factor loadings smaller than 70.225 are not given)
PC1 PC2 PC3 PC4
As F F F 0.778
Cr F F 0.553 0.690
Cu F F 0.792 FCd F F 0.802 F
Pb 0.593 F 0.601 F
Mn F F 0.747 0.476
Zn 0.396 F 0.801 F
V F F 0.295 0.758
Ni 0.279 0.320 0.712 0.229
Fe F 0.541 0.525 0.513
Ph 0.232 0.876 F F
An 0.640 0.510 F F
Fl 0.445 0.790 0.294 F
Py 0.376 0.843 F F
B[a] !An 0.551 0.718 F F
Chry 0.921 0.296 F F
B[e]Py 0.920 0.290 F F
B[b]Fl 0.893 0.395 F F
B[k]Fl 0.886 0.357 F F
B[a]Py 0.960 F F F
dB[a;h]An 0.948 F F FB[ghi]Pe 0.804 0.401 F F
I[1,2,3cd]Py 0.937 0.301 F F
Variance % 37.0 17.8 17.3 12.7
Source type Vehicle Diesel Road dust Fuel oil
Table 5
Rotated principal component matrix for coarse aerosol (factor loadings smaller than 70.225 are not given)
PC1 PC2 PC3 PC4 PC5
As 0.439 F 0.448 0.543 0.394
Cr F F 0.730 F 0.630
Cu F F 0.396 0.872 F
Cd F F F 0.644 F
Pb 0.297 F 0.617 F F
Mn F F 0.554 0.696 F
Zn F F 0.836 F F
V F F 0.725 0.252 F
Ni 0.338 0.387 F F 0.602
Fe F F 0.878 F F
Ph 0.340 0.818 0.291 F F
An 0.834 0.405 F F FFl 0.477 0.806 F F F
Py 0.354 0.812 0.251 F F
B[a] !An 0.423 0.630 0.424 F F
Chry 0.951 F F F F
B[e]Py 0.847 F F F F
B[b]Fl 0.857 F 0.225 F F
B[k]Fl 0.902 0.353 F F F
B[a]Py 0.971 0.266 F F F
dB[a;h]An 0.954 F F F FB[ghi]Pe 0.842 0.368 F F F
I[1,2,3-cd]Py 0.926 0.233 F F F
Variance % 37.4 14.0 13.3 13.3 7.2
Source type Vehicle Diesel Road dust Industrial Fuel oil
E. Manoli et al. / Atmospheric Environment 36 (2002) 949961956
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Fig. 4. Mean source contribution to fine aerosol.
E. Manoli et al. / Atmospheric Environment 36 (2002) 949961 957
8/3/2019 2001. Chemical Characterization and Source Identification Apportionment of Fine and Coarse Air Particles
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Fig. 5. Mean source contribution to coarse aerosol.
E. Manoli et al. / Atmospheric Environment 36 (2002) 949961958
8/3/2019 2001. Chemical Characterization and Source Identification Apportionment of Fine and Coarse Air Particles
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emissions (source of Pb), diesel engines (source of Cu),
etc. (Samara et al., 1994a; Swietlicki et al., 1996;
Thurston and Spengler, 1985; Hildemann et al., 1991).
The fourth PC was loaded on V, As, Fe, Mn, Cr and
moderately on Ni. Arsenic is usually considered as coal
burning tracer, while oil combustion has been reported
as been characterized primarily by Ni and V andsecondarily by Fe and Mn (Harrison et al., 1996;
Swietlicki et al., 1996; Miranda et al., 1996; Samara
et al., 1994a). Given that coal burning in our area is very
limited occurring only in few small-sized industrial
activities (e.g. non-ferrous metal smelters), whereas oil
burning is used for both space heating and industrial
purposes, PC4 was selected to represent oil combustion.
In the coarse particle data set, five PCs were obtained
with eigenvalues >1 explaining 85% of the total
variance. Four of them, PC1, PC2, PC3 and PC5
showed similar loading patterns with PC1, PC2, PC3
and PC4 of the fine particle data set, thus they wereinterpreted as vehicle, diesel, road dust and oil combus-
tion source types, respectively. The fourth PC was
primarily loaded on Cu, Cd, Mn and As and secondarily
on V. This PC was interpreted as representing emissions
from several metallurgical activities occurring in the
industrial area (Samara et al., 1994a).
The multiple regression of aerosol and individual
constituent masses on APCS exhibited good correlation
between observed and predicted values with correlation
coefficients in the range 0.680.99. In cases that a
regression constant significant at the 0.05 level was
derived, it was interpreted as representing unidentified
sources. Mean source contributions to fine and coarse
aerosol are shown in Figs. 4 and 5, respectively. Results
showed that the largest contributor to aerosol mass in
the fine size fraction is traffic with a total contribution
38%, whereas road dust clearly dominated the coarse
size fraction. Vehicular emissions appeared to be the
unique source of fine-sized PAHs, whereas coarse-sized
PAHs were additionally originated from road dust, coal
fired non-ferrous metal smelters and oil combustion.
Road dust was found to be stronger contributor to fine
and coarse Pb than vehicular emissions. These findings
are different from those reported by Harrison et al.
(1996) for Birmingham, where road dust was unexpect-edly found to be the major contributor to PAHs, while
direct traffic emissions to Pb. As mentioned, sometimes
these two sources are incompletely separated by PCA as
road dust particles are resuspended mainly due to
vehicular movements (Harrison et al., 1996; Okamoto
et al., 1990). Lin et al. (1999), using B[e] Py as an
indicator, estimated the contribution of traffic to the
concentration of 47 ring PAHs in Birmingham city
centre at 8082%, while 6084% of the total PAH traffic
emissions was attributed to diesel vehicles. On the
contrary, non-catalytic gasoline vehicles were found to
be by far the largest contributor of PAHs in Los Angeles
basin, despite the overwhelming contribution of diesel
exhausts to the fine mass (33% vs. 6% for gasoline
vehicles) (Schauer et al., 1996).
The source apportionment findings of this study are in
general agreement with the majority of reported data,
which point out traffic emissions and traffic-induced
road dust resuspension as the major sources of fineurban aerosol with sum contributions up to 80%
(Okamoto et al., 1990; Miranda et al., 1996, 2000;
Harrison et al., 1996; Alonso et al., 1997; Schauer et al.,
1996).
The source types identified in this study are similar to
those found in a previous receptor modelling exercise
carried out in Thessaloniki, the relative contribution of
sources are, however, different since previous modelling
was not oriented to specific aerosol fractions but to total
suspended particles (Samara et al., 1994a, b). It is
believed that current apportionment results will be
useful to the local authorities to regulate air PM.
4. Conclusions
The distribution of particle mass, trace element and
particle-bound PAH concentrations in the fine
(o3.0 mm) and coarse (>3.0mm) size fractions was
investigated at a trafficked-site in Thessaloniki, Greece.
7676% on average of the total ambient aerosol mass
was distributed in the fine size fraction. Fine-sized trace
elemental fractions ranged from about 50% for Fe and
Mn up to 95% for Zn. The fine-sized PAH fractions
were between 95% and 99% for all species.
The size distribution of aerosol mass exhibited
significant seasonal dependence with a shift to larger
fine fractions in winter. Similar seasonal trend was
exhibited by PAHs, whereas larger fine fractions in
summer were shown by trace elements.
The compositional signature of local paved-road dust
was found to be strongly correlated to that of coarse
particles thus suggesting significant contribution of
resuspended road dust to this particle fraction.
A multivariate receptor model (multiple regression on
absolute principal component scores, MR/APCS) ap-
plied on separate fine and coarse aerosol data enabledmajor source types to be identified and apportioned:
gasoline and diesel emissions, road dust, metallurgical
processes and oil combustion. Traffic was found to be
the largest contributor to fine-sized aerosol (total
contribution 38%) followed by road dust (28%). Road
dust clearly dominated the coarse size fraction (57%).
Acknowledgements
The authors wish to thank the Secretariat for Science
and Technology, Ministry of Development, and the
E. Manoli et al. / Atmospheric Environment 36 (2002) 949961 959
8/3/2019 2001. Chemical Characterization and Source Identification Apportionment of Fine and Coarse Air Particles
12/13
Organization for the Master Plan Implementation and
Environmental Protection of Thessaloniki for research
funding. They are also grateful to Prof. V. Simeonov,
Kliment Ohridski University, Sofia, Bulgaria for
useful comments on receptor modelling.
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