ARTICLE IN PRESS

AE International – Europe

Atmospheric Environment 38 (2004) 4437–4446

The role of atmospheric dispersion in the seasonal variation

of PM1 and PM2.5 concentration and composition in the
urban area of Milan (Italy)
R. Vecchia,b,*, G. Marcazzana,b, G. Vallia,b, M. Ceriania, C. Antoniazzia
a
Istituto di Fisica Generale Applicata, University of Milan, Via Celoria 16, 20133 Milan, Italy
b
Istituto Nazionale di Fisica Nucleare, Section of Milan, Via Celoria 16, 20133 Milan, Italy
Received 13 February 2004; received in revised form 6 May 2004; accepted 26 May 2004

Abstract

The seasonal variation of PM1 and PM2.5 mass concentration and composition has been investigated in the great
urban area of Milan. PM samplings were carried out 3 times a week during the year 2002. Mass and elemental
concentrations were measured in all samples and in a limited number of filters also the elemental and organic carbon
contribution (EC and OC) was determined.
In the urban area of Milan, PM2.5 comprises about 60% and 70% of the PM1 mass in summer and in winter,
respectively. Among the measured PM components carbon compounds and sulphates are by far the major contributors and
a significant contribution likely due to nitrates (not measured) should also be considered. PM1 and PM2.5 concentration
and composition show a strong seasonal behaviour, which was studied in relation to atmospheric dispersion conditions.
Our approach is based on the use of Radon concentration as a natural tracer of differences in the average mixing
layer height during the year. The application of a suitable ‘‘Radon index’’ allows the normalisation of PM mass and
elemental data to account for the seasonal effect due to differences in atmospheric dispersion conditions.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: PM1; PM2.5; Elemental composition; Radon

1. Introduction In the last 10 years concern on particulate matter

Fine aerosol particles (e.g. PM2.5 and PM1) have
been found to play a key role in global climate change,
in pollution problems and in health hazard. They affect
the natural energy balance of the Earth mainly by
reflecting/absorbing solar radiation and influencing the
reflective and absorbing properties of clouds. The study
of the large-scale influence of aerosols on climate needs
a deep knowledge of smaller particles and of their
variations in size, chemical composition, distribution in
time and space and residence times (IPCC, 2001).
*Corresponding author. Fax: +39-02-503-17496.
E-mail address: roberta.vecchi@unimi.it (R. Vecchi).
(PM) concentration values in urban areas led to a
number of European studies on PM10 (Hoek et al.,
1997; Art"ıñano et al., 2001) that is currently the
European standard (EU Directive 99/62) for air quality
assessment. A few years ago, the European Community
encouraged all Member States to gather preliminary
data on PM2.5, so that many research groups began a
characterisation of this PM fraction (Borbély-Kiss et al.,
1999; Querol et al., 2001; Marcazzan et al., 2001; Hoek
et al., 2002). Epidemiological studies and research on the
mutagenic effects of airborne particulate matter point at
the adverse health effects of fine particles (Dockery et al.,
1993; Schwartz et al., 1996; Samet et al., 2000;
Katsouyanni et al., 2001) as they are able to reach deep
lung regions and are vehicles of toxic substances.

1352-2310/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2004.05.029
 ARTICLE IN PRESS
4438 R. Vecchi et al. / Atmospheric Environment 38 (2004) 4437–4446
Moreover, several authors detected mutagenic com-
pounds almost exclusively located on particles with
aerodynamic diameter lower than 2 mm (van Houdt,
1990; Pagano et al., 1996).
As a consequence of the growing interest of the
scientific community in PM finer fractions and of the
lack on PM1 data in Europe, in 2001 we started a
temporal extended study on PM1 to obtain statistically
significant data on this PM fraction. Indeed, previous
research carried out in the Milan area (Marcazzan et al.,
2001) revealed a strong seasonal variation of PM10 and
PM2.5 concentrations with the highest values during
winter months (especially December, January and
February). Wintertime PM10 levels often exceeded the
EU limit value established for health protection not only
in Milan but also at many other urban areas in the Po
valley (Marcazzan et al., 2002). In Milan, daily gravi-
metric measurements performed by one of the monitor-
ing stations belonging to the regional air pollution
network registered 66 mg m 3 for PM10 and 43 mg m 3
for PM2.5 as average concentrations during the year
2002. Moreover, 177 exceedences of the EU PM10 limit
value of 50 mg m 3 were observed (ARPA, 2002). These
data stress the importance of a deeper knowledge of PM
composition, of emission sources (number and type) and
of the role of atmospheric dispersion conditions in the
Milan area as well as in the whole Po valley.
During our monitoring campaign co-located measure-
ments of PM1 and PM2.5 (and once a week additional
PM10 samplings) were performed to relate PM1 to other
PM fractions and to insert these new data in a wider
research context.
The aim of the research was twofold:
* to assess concentration levels, main components,
mass closure, major sources and seasonal variability
of PM1 and PM2.5;
* to study the role of average atmospheric dispersion
conditions on PM concentration and composition in
the two seasons and to single out the importance of
seasonal variations in source emissions and in
secondary aerosol formation mechanisms. To inves-
tigate on this point we performed measurements of
the 222Rn concentration in outdoor air and obtained
an index to account for seasonal variations of the
atmospheric dispersion conditions.
2. Area of investigation
2.1. Site
Milan is in Northern Italy and it is located in centre of
the Po valley, which is the most industrialised and
populated part of the country. It is the second Italian city
(after Rome) for population and its geographical
position makes it the greatest trade junction in Italy.
The urban area covers 181 km2 and has 1,307,000
inhabitants; the territorial extension of the Milan
province is 1980 km2 (652 km2 of urban areas and
102 km2 of industrial settlements) and the population
rises up to 3,737,000 inhabitants. The number of
passenger cars circulating daily in the province is
2,231,280 (0.62 vehicles/inhabitant); in addition, 4000
buses and a very high number of heavy duty vehicles for
goods transport must be also taken into account (Galileo
Ambiente, 2002).
The urban area of Milan is characterised by many
residential and commercial premises and a very high
volume of vehicular traffic. Moreover, many industries
including chemical and metallurgical factories, incinera-
tors, refineries and power plants are located in its outskirts.
In Milan, a large conversion to methane as fuel for
domestic heating is in progress. According to the estimate
of atmospheric emissions (for criteria pollutants, year
2000) from different sources in the municipality of Milan
(Galileo Ambiente, 2002) the main sources contributing to
primary PM10 are traffic (72%), domestic heating (21%)
and incinerators (5%). NOx emissions in the city are due
to traffic (66%), domestic heating (23%), industry (8%)
and incinerators (3%). SO2 is mainly emitted by the
domestic heating source (86%) and by traffic (10%).
However, the SO2 emission in the municipality of Milan is
about 3% of that registered at a regional scale, which
likely contributes to background aerosol formation.
Anthropogenic VOC emissions in the urban area are
mainly due to solvent use and traffic (about 50% and
41%, respectively). NH3 is emitted at a regional scale by
agricultural and breeding activities (about 97%).
2.2. Climate
In the Po valley the climate is typically continental
although mitigated by the influence of the Adriatic sea and
by the shielding of the Alps. The atmospheric circulation is
often stagnant over the Po valley especially during
wintertime, when frequent thermal inversions at low
altitude, low mixing layer heights and prolonged foggy
or hazy periods occur. In Milan the wind speed is generally
low, the average wind speed was 1.5 m s 1 during winter
and 1.8 m s 1 during summer 2002. A high rainfall rate (in
excess of 400 mm compared with the average of 1000 mm
observed during the last decade) was also registered in the
monitored area during the year 2002, especially in
February, May and November (ARPA, 2002).
3. Material and methods
3.1. Aerosol sampling and mass determination
The sampling site is located in the campus of our
University, which is approximately 2 km far from the
 ARTICLE IN PRESS
R. Vecchi et al. / Atmospheric Environment 38 (2004) 4437–4446
city centre. It is placed in residential and commercial
area and the average traffic volume can be considered
typical for the whole urban area. The sampling platform
is placed on the roof of our Institute (at a height of
about 10 m a.g.l.) and it can be considered quite
representative of the average air pollution in the
investigated area as it is not a kerbside station. This
location allows comparisons with PM data obtained
during previous campaigns and the monitoring of PM
temporal trends in Milan (Marcazzan et al., 2001, 2003).
The co-located PM1 and PM2.5 samplings were
carried out in the year 2002 during the summer period
(Jun–Sept) and the winter semester (Jan–March and
Oct–Dec). PM1 and PM2.5 were sampled for 24 h at
fixed days (Tuesday–Thursday–Sunday), 107 PM1 and
105 PM2.5 samples were collected. CEN-equivalent
samplers (according to the European norm EN12341,
CEN=Comité Européen de Normalisation) were
equipped with PM2.5 and PM1 inlets. Before and after
the samplings the PTFE filters were exposed for 24–48 h
on open but dust-protected sieve-trays in an air-
conditioned weighing room (T=2272 C and
R.H.=4375%). The gravimetric determination of the
mass was carried out using an analytical microbalance
(precision 1 mg), which is installed and operates in the
weighing room. Calibration procedures check the
microbalance performance. According to our weighing
laboratory protocol both before and after sampling,
each filter is weighed at least twice to obtain one mass
measurement result. The two readings have to agree
within 5 mg to be accepted; if the second measurement is
more than 5 mg apart from the first, a new pair of
weighing is immediately done until they are within
the75 mg goal.
Meteorological parameters (temperature, pressure,
relative humidity, solar radiation, rainfall, wind speed
and direction) were available from the meteorological
station located at our Institute.
3.2. Analytical techniques
Energy dispersive X-ray fluorescence analysis was
performed on all aerosol samples determining major,
minor and trace elements. Routinely Al, Si, S, Cl, K, Ca,
Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Pb
concentrations were measured. The minimum detection
limit (mdl) was in the range 1–10 ng m 3 for different
elements. Micromatter standard reference samples
(Micromatters, US) were used for the quantitative
calibration of the system. A check of the calibration was
periodically performed analysing the NIST standard
SRM2783 (Air Particulate on Filter Media).
The data acquisition, storage and reduction was
supervised by a programme on a personal computer,
the analysis of X-ray spectra was performed using the
Axil code (Van Espen et al., 1977). Experimental errors
4439
were estimated to be about 10–15%. Details on the
XRF system set-up can be found elsewhere (Marcazzan
et al., 2001, 2004).
In a limited number of samples, elemental carbon
(EC) and organic carbon (OC) were measured by the
Sunset Laboratory Inc., USA, using a thermo-optical
transmission method described in Birch and Cary
(1996).
3.3. The radon measurement: an indicator of atmospheric
dispersion
The Radon hourly concentration is routinely and
continuously measured at ground level (6 m asl) in
Milan by our group. Radon activity concentration
outdoor is detected with hourly resolution through the
collection of its short-lived decay products attached to
aerosol particles and the spectroscopic evaluation of
their alpha activity (estimated detection limit=
0.2 Bq m 3). Details on the experimental methodology
to measure 222Rn concentration are reported in Sesana
et al. (2003).
The seasonal variation observed in PM concentrations
with high values during winter has been also registered
for a number of gaseous pollutants (e.g. SO2, NOx, CO,
BTX,...) and for the atmospheric concentration of
Radon and its progeny. Long-term Radon measure-
ments (Kataoka et al., 1998; Perrino et al., 2001; Sesana
et al., 2003) show that the temporal variation of its
concentration can give immediate information on the
evolution of the stability conditions in the boundary
layer. The stability conditions of the lower atmospheric
layers, on a local scale, are very important as influence
pollutants concentration on different time scales (emis-
sion rates, chemical transformations and deposition
processes must also be taken into account). The dilution
of pollutants in the mixing layer must be ascribed to
thermal and dynamic turbulence, whilst the horizontal
transport of pollutants is due to the wind field. In the
Milan area and in the whole Po valley, ventilation is
scarce (despite sporadic advection episodes, typically
Föhn events extensively described in Gandino et al.,
1990) and vertical dispersion plays the main role.
Radon can be considered a good natural tracer of
vertical dispersion as it does not undergo chemical
transformations in the air and it has a half-life of 3.8
days that is long enough to measure the atmospheric
phenomena of interest here. It also has an approxi-
mately constant rate of exhalation from the ground over
large, homogeneous areas and over time.
Long-term measurements performed in Milan by our
group exhibit two typical patterns related to an hourly
and a monthly time-scale. In the first case, Radon
concentrations are frequently characterised by a mini-
mum in late afternoon and a maximum in the early
morning. In Fig. 1, as examples, the daily mean Radon
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4440 R. Vecchi et al. / Atmospheric Environment 38 (2004) 4437–4446

Radon mean daily pattern

30
jan2002
222 Rn concentration (Bq/m3)

25
jul2002
20

15

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
Hour
Fig. 2. 222Rn monthly average concentration and monthly
Fig. 1. 222Rn typical daily concentration pattern (in Bq m 3), minimum average concentration (in Bq m 3), year 2002, Milan.
January and July 2002, Milan.

concentrations are reported for January and July 2002. The winter/summer ratio between average Radon
This pattern is observed on sunny days with clear sky minimum concentrations during the years 2000–2002
(both during day and night) and low ventilation rate. appears to be steadily assessed at 2.0–2.1. The PM
The nocturnal accumulation of Radon is due to the low measurement campaign here described does not cover
mixing layer caused by a ground-based temperature homogeneously the whole year 2002 so that the ratio R
inversion of radiative origin. The variation of Radon has been calculated only for the sampling days (R=1.8
concentration observed between the minimum in the for PM1 samples and 1.7 for PM2.5 samples). This ratio
afternoon and the maximum in the following day is a has been calculated using a Radon average minimum
good indicator of the nocturnal mixing layer depth. value of 4.5 Bq m 3 for both PM1 and PM2.5 samplings
When the sun rises in the morning and heats the during the summer period and of 8.1 Bq m 3 for PM1
ground the inversion is destroyed so that the re-mixing and 7.8 Bq m 3 for PM2.5 data-series during the winter
of Radon takes place in layers of increasing heights semester.
causing a decrease of its concentration levels. The In the following, we will use the ratio R as a
minimum concentration is registered during the after- ‘‘normalisation’’ factor which removes the seasonal
noon when the mixing layer reaches its maximum depth. effect due to differences in atmospheric dispersion
The variation between maximum and minimum Radon conditions from PM mass and element concentrations.
concentration in the same day is an index of the This approach allows the evaluation of differences in
maximum height of the mixing layer. the contribution from emission sources for aerosol of
The other Radon typical pattern refers to a seasonal primary origin and reveals variations in the strength of
behaviour (with higher concentrations in winter than in production mechanisms for PM of secondary origin in
summer) observed on monthly Radon concentration. the two seasons.
Fig. 2, displays monthly averages of daily Radon
concentrations and monthly averages of daily minima
measured in the year 2002. Higher Radon minimum
concentrations registered during wintertime reflect the 4. Results and discussion
lowering of the upper limit of the mixing layer height
whereas lower Radon minima observed during summer- 4.1. Mass concentration
time indicate an increase of the upper limit of the mixing
layer depth. PM1 and PM2.5 daily values show variations mainly
In this paper the ratio R between wintertime and related to differences in the atmospheric dispersion
summertime average minimum Radon concentrations conditions. Large seasonal differences can be also
has been taken as an index of seasonal differences in observed in the data-base with PM1 and PM2.5 highest
mean dispersion conditions of the atmosphere. It gives concentrations during winter. The average concentra-
information on the average ratio between the maxima tion is 16.478.3 mg m 3 for PM1 and 27.2714.1 mg m 3
heights of the mixing layer in the two seasons because for PM2.5 during the summer period (June–July–
the minimum Radon concentration is registered when September) and it is 41.0718.4 mg m 3 for PM1 and
the mixing layer is well developed and the atmospheric 58.6729.5 mg m 3 for PM2.5 during the winter semester
dilution is at its maximum. The minimum Radon (Jan–March and Oct–Dec). On average, 30% and 40%
concentrations have been chosen as PM is not produced of the PM2.5 mass is in the PM(2.5–1)—‘‘intermodal’’—
by sources with constant emission but its dominant fraction (obtained by subtraction using PM2.5 and PM1
primary sources (typically traffic and anthropogenic co-located measurements) during the winter semester
activities) are active mainly during daytime hours. and the summer period, respectively.
 ARTICLE IN PRESS
R. Vecchi et al. / Atmospheric Environment 38 (2004) 4437–4446 4441

It is interesting to note that during the month of
August (not included in the summer period average,
given above), PM1 concentration is 10.373.9 mg m 3
and PM2.5 is 18.776.5 mg m 3. These concentrations
are likely to be considered the ‘‘background urban’’
levels for the area of Milan. Indeed, during August there
is a huge decrease of traffic and industrial activities (see
also differences in the elemental concentrations pre-
sented in Table 1) owing to summertime holidays, which
are, in Italy, traditionally spent in this month. The
assessment of urban background particulate matter level
can be a useful information in provision of setting EU
limit values for PM2.5.
In the urban area of Milan, PM1 constitutes about
60% and 70% of the PM2.5 mass in summer and in
winter, respectively. Estimates of the PM1/PM10 and
PM2.5/PM10 ratios were also carried out on a limited
number of samples as PM10 was monitored once a week
(on Thursday) during the campaign. PM1 is a significant
part of PM10 (35% in summer and 53% in winter) and
PM2.5/PM10 ratio is 0.77 during the winter semester
and 0.63 during the summer period. The PM2.5/PM10
average ratios are in agreement with those registered in a
previous campaign performed at the same location for
the whole year 2001 (Marcazzan et al., 2003).
Separating the PM data-base into week-days and
week-ends a detectable decrease in PM2.5 concentra-
tions ( 35% in summer and 10% in winter) during the
week-ends comes out. On the contrary, the reduction in
PM1 concentration levels is almost negligible ( 1.5%)
during wintertime and it is 14% during summertime;
these lower percentages are probably due to PM1 longer
residence times in the atmosphere.
The influence of local meteorological conditions on
fine particulate matter concentrations has been also
studied focusing on windy and rainy days. A slight effect
( 10%) due to rainfall can be observed on both
fractions while a more significant decrease of PM1 and
PM2.5 levels (20–35%) appears during days with wind
velocity higher than 2 m s 1. Similar meteorological
influences were also observed in PM10 and PM2.5
concentrations registered at the same location during a
previous study (Marcazzan et al., 2003).
The normalisation of PM mass using the ‘‘Radon
index’’ has been carried out to account for the seasonal
effect due to differences in dispersion conditions. The
PM1 normalised mass concentration (see also Fig. 4) is
about 40% higher in winter than in summer (in PM2.5
mass this percentage is 30%). This result evidences the
presence of additional sources during the cold season
(e.g. domestic heating) and the influence of low
temperatures typical of the cold season. Low tempera-
tures favour the aerosol particle phase in respect of the
gaseous one in the formation of secondary aerosol and

Table 1
PM1 and PM2.5 average values of the elemental concentrations (ng m 3) shown separately for the winter semester (Oct–Mar), for the
summer months (Jun–Jul–Sep) and for August

PM1 (ng m 3) PM2.5 (ng m 3)

Winter 2002 Summer 2002 August 2002 Winter 2002 Summer 2002 August 2002

n.samples 56 38 11 53 33 16
Mass 41000718400 1640078300 1030073900 58600729500 27200714100 1870076500
Al 1678 (54) 1475 (9) 1772 (2) 53729 (53) 49727 (30) 47720 (14)
Si 42720 (56) 30712 (37) 2779 (11) 116790 (53) 116764 (33) 92742 (16)
S 12977516 (56) 14457721 (38) 9577424 (11) 19427972 (53) 187671022 (33) 17077778 (16)
Cl 2897199 (56) 37715 (6) omdl 4087312 (53) 28721 (10) omdl
K 2577115 (56) 81748 (38) 63738 (11) 3427180 (53) 124757 (33) 119757 (16)
Ca 24710 (39) 1777 (38) 1174 (11) 69754 (50) 65728 (33) 48714 (16)
Ti 773 (42) 471 (9) 371 (5) 1477 (53) 875 (31) 672 (16)
V 572 (54) 472 (18) 371 (6) 774 (47) 572 (25) 372 (13)
Cr 271 (36) 171 (25) 171 (5) 573 (44) 372 (30) 271 (13)
Mn 976 (56) 472 (38) 371 (11) 18712 (52) 875 (33) 572 (16)
Fe 89739 (56) 42723 (38) 2477 (11) 3097205 (53) 186787 (33) 120738 (16)
Ni 774 (56) 271 (37) 171 (9) 975 (53) 271 (33) 271 (16)
Cu 774 (56) 373 (38) 271 (11) 18711 (53) 1076 (33) 672 (16)
Zn 66734 (56) 32720 (38) 1677 (11) 135798 (53) 66741 (33) 25713 (16)
As 271 (49) 171 (24) 171 (3) 372 (45) 271 (24) 171 (7)
Se 271 (42) 171 (30) 171 (5) 371 (37) 271 (27) 171 (13)
Br 975 (56) 372 (38) 271 (11) 1377 (53) 472 (33) 472 (16)
Pb 35720 (56) 15712 (38) 875 (11) 55735 (53) 22713 (33) 1377 (16)

In parenthesis the number of samples above the minimum detection level (mdl) is given.
 ARTICLE IN PRESS
4442 R. Vecchi et al. / Atmospheric Environment 38 (2004) 4437–4446

the stability of particulate NH4NO3 in the atmosphere

(Strader et al., 1999; Putaud et al., 2004).

4.2. PM elemental characterisation and composition

PM1 and PM2.5 elemental average concentrations (in

ng m 3) are given in Table 1 separately for the winter
semester (Oct–Mar), for the summer period (Jun–Jul–
Sep) and for August.
The sum of all elements detected by ED-XRF explains
only a little part of the mass of fine particulate matter
(about 10% in summer and 5% in winter for both
Fig. 3. partitioning of element concentration between PM(2.5–
fractions), suggesting that the greatest contribution
1) and PM1 during summertime (S) and wintertime (W) in
should be ascribed to light elements as H, C, N, O not Milan, year 2002.
determined. In both fractions the most abundant
element is Sulphur whose average values are about
1400 ng m 3 in PM1 and 1900 ng m 3 in PM2.5,
independently of the season. All the other elements
have concentrations much lower than S both in PM1
and PM2.5 (from a few hundreds of ng m 3 down to a
few ng m 3) and, as a common feature, show a seasonal
effect characterised by wintertime values much higher
than summertime ones.
Comparing the elemental concentration data regis-
tered in August with those measured in the summer
period, a general decrease during August can be noted
with a strong reduction of some elements such as Fe, Zn Fig. 4. PM1 and PM2.5 element concentrations normalised
and Pb (tracers both of industrial processes and traffic) using the ‘‘Radon index’’, the winter/summer ratio is
which halve their concentration levels. As already represented.
observed for mass concentrations, August is quite an
untypical month for the Milan urban area and the mass
and elemental concentrations detected during this
period can be considered representative of ‘‘urban PM2.5. This result can be explained considering the
background’’ as anthropogenic activities are at their strong photochemical activity registered during sum-
minimum. mertime in Italy that enhances the conversion of SO2 to
Fig. 3 displays the partitioning of elemental concen- sulphates. As pointed out in previous research (Mar-
trations between the intermodal, PM(2.5–1), and the cazzan et al., 2001, 2003; Putaud et al., 2002) in the Po
sub-micronic, PM1, fractions of PM2.5 during the two valley a large contribution to S levels is given by
seasons. Some elements (i.e. S, K, V, Ni, Br, Pb) with a sulphates, and in particular by ammonium sulphate,
dominant anthropogenic origin are found preferably in mostly originated over a regional scale. On the contrary,
the sub-micronic fraction of PM2.5 and do not exhibit Potassium normalised concentrations appear to be 50%
any appreciable seasonal effect. Al, Si, Ca and Ti (PM2.5) and 70% (PM1) higher during the winter
measured in the intermodal fraction account for about semester; this effect is likely due to emissions from
60–70% of their concentration in PM2.5 indicating a domestic heating (which comprehend also wood com-
contribution from soil dust as evidenced also by Kegler bustion) (Currie et al., 1994; Chow, 1995; Kim et al.,
et al. (2001). In the intermodal fraction an increase of 2003). Bromine concentration has a winter/summer ratio
about 10% during the summer is detectable for Al, Si, (normalised to Radon index) which is 1.5 owing to the
K, and Fe. In the sub-micron sized particles an Br volatilisation (Harrison and Sturges, 1983) during
uncertainty about the origin of Al, Si and Ca arises, as summertime. The high value of the winter/summer ratio
they can be due to soil dust or cement dust as well as to found for Ni and Pb suggests a seasonal difference in
impurities in automotive exhaust emissions. emission from sources not yet identified. Al, Si and Ca—
To account for the atmospheric dispersion conditions elements typical of the mineral dust—show higher
the elemental concentrations were normalised using the normalised concentrations in both fractions during the
Radon index (Fig. 4). The summertime Sulphur normal- summer months as re-suspension can be favoured by
ised concentration appears to be higher than the drier soils. The winter/summer ratio of normalised
wintertime one by a factor two in both PM1 and concentration calculated for the remaining elements is
 ARTICLE IN PRESS
R. Vecchi et al. / Atmospheric Environment 38 (2004) 4437–4446
about 1 with a 10–20% variability, indicating that most
of the seasonal effect affecting the elemental concentra-
tions reported in Table 1 has an explanation in
differences in atmospheric dispersion conditions.
For the purpose of mass closure an estimation of
some PM components (sulphates, mineral dust, and
heavy metal oxides) has been carried out using the
elemental concentrations detected on all available
samples. Sulphur has been considered mainly in the
form of ammonium sulphate. Mineral dust is given by
the sum of Al, Si, K, Ca, Ti and Fe oxides (15% of the
total is generally added to account for Na and Mg
oxides, not detected) (Eldred et al., 1987). The heavy
metals component has been computed by the sum of Fe,
Cu, Zn and Pb oxides. Further details on the methodol-
ogy used to evaluate these contributions can be found in
Marcazzan et al. (2001). Results are summarised in
Table 2 where the percentage contribution of these
components to the PM mass is given. In order to reach a
complete mass closure, a few specific PM1 and PM2.5
samplings (two weeks during both seasons) to determine
the elemental and organic carbon concentration were
also performed. The obtained percentages of elemental
and organic carbon were inserted in Table 2 with the
other PM components (calculated on the whole data set)
assuming that, although determined on a few samples,
they could be considered quite representative. The
organic carbon (OC) concentrations were converted
into organic compounds (OC) concentrations using a
mean molecular-to-carbon ratio of 1.6, as proposed by
the recent literature for urban areas (Salma et al., 2004;
Turpin and Lim, 2001).
The major contributor to PM mass is organic matter,
the OC percentages range between 37.3% and 46.8% in
PM2.5 and between 37.3% and 43.3% in PM1 during
summer and winter, respectively. The EC contribution
to the PM2.5 mass is 8.8% during the summer period
and 4.8% during the winter semester. EC percentages of
7.9% and 5.7%, in summer and winter, respectively, are
found in PM1. These preliminary EC and OC data are in
Table 2
Wintertime and summertime PM1 and PM2.5 mass (in mg m 3) and the percentage contribution of some PM components (ammonium
sulphate, mineral dust, heavy metal oxides, OC and EC)
PM1
Summer 2002
3
Mass (mg m ) 16.4
Ammonium sulphate (%) 36.4
Mineral dust (%) 0.7
Heavy metal oxides (%) 0.6
OC (%) 37.3
EC (%) 7.9
Others (%) 17.1
The undetected mass has been named ‘‘Others’’ (likely due to nitrates and minor components such as water).
4443
good agreement with those reported by Putaud et al.
(2002) for the submicron aerosol measured during the
PIPAPO field campaign. The OC/EC ratio calculated on
the few samples is between 5 and 6 during wintertime
and much lower (2.6–3) during the summer period.
Literature data (Chow et al., 1993; Turpin and
Huntzincker, 1995; Strader et al., 1999) show that OC/
EC ratios higher than 2–2.5 are indicators for secondary
organic aerosol formation; therefore, our OC/EC
preliminary values indicate that, on average, secondary
organic aerosol production is significant in Milan.
The second contributor to PM2.5 and PM1 mass is
ammonium sulphate, which accounts for 28–36% in
summer and for about 13% in winter. The mineral dust
component explains a small part of the mass (0.5–2%)
and shows higher percentages during the summer period
as already evidenced for soil-related elements’ concen-
trations. Also the contribution of heavy metal oxides to
the mass is almost negligible (about 0.5–1.5%) in both
fractions but metal concentrations are significant in
relation to their potential toxicity (Gilmour et al., 1996;
Apostoli, 1999). The unaccounted mass fraction (called
‘‘Others’’) is thought to result from nitrates and minor
components (i.e. aerosol-bound water) and shows higher
percentages during the cold season (32.6% in PM2.5 and
36.8% in PM1). These percentages are in line with
nitrate data obtained in the Po valley (Schaap et al.,
2002; Putaud et al., 2002), which indicate Northern Italy
as one of the European areas with very high nitrate
levels during winter. Because of the semi-volatile nature
of nitrates during the summer their contribution
strongly diminishes (down to 17–22%).
Wintertime/summertime concentrations normalised
to Radon index are represented in Fig. 5 for the
evaluated components. The TC (=EC+OC) repre-
sents the Carbon compounds contribution made of EC
and organic compounds (OC). The winter/summer
ratio of TC normalised component is 1.5 indicating a
higher contribution of carbon compounds during the
winter season. It is likely due to the lower temperatures
PM2.5
Winter 2002 Summer 2002 Wintertime 2002
41.0 27.2 58.6
13.0 28.4 13.7
0.5 2.1 1.0
0.7 1.3 1.1
43.3 37.3 46.8
5.7 8.8 4.8
36.8 22.1 32.6
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4444 R. Vecchi et al. / Atmospheric Environment 38 (2004) 4437–4446
Fig. 5. PM components (TC=OC+EC, ammonium sul-
phate, mineral dust, heavy metal oxides) normalised using the
‘‘Radon index’’; the winter/summer ratio is represented.
which favour the aerosol particle phase of organic
compounds and to the low mixing layer heights which
allow the accumulation of gaseous precursors and the
acceleration of secondary organic aerosol formation
(Strader et al., 1999). As already found for the normal-
ised sulphur concentration, the ammonium sulphate
component normalised to the Radon index evidences a
strong increase (approximately a factor 2) during the
summer period pointing at the importance of atmo-
spheric photochemical transformations. Also mineral
dust increases (more in PM2.5 than in PM1) during
summertime because of the soil dryness as already noted
for soil-related elements. The smallest winter/summer
variation in normalised components is observed for
heavy metal oxides indicating that their anthropogenic
sources (mainly traffic and industrial activities) do not
vary so much with the season.
5. Conclusions
In this paper data on PM1 and PM2.5 mass
concentration and composition are given for Milan,
the greatest urban area in Northern Italy. Results
obtained from this campaign are of interest because
information on the sub-micronic fraction of particulate
matter is scarce or still lacking in Europe. In Milan,
PM1 contributes significantly (60–70%) to PM2.5 mass
increasing the concern for PM health hazard. The mass
of the sub-micronic fraction is mainly composed of
anthropogenic components (i.e., heavy metals, organics,
sulphates,...) enhancing PM1 potential toxicity.
The investigation focuses on the role played by
atmospheric dispersion conditions in determining the
seasonal variation observed in PM mass and composi-
tion. In particular, the use of a suitable ‘‘Radon index’’
allows the normalisation of PM mass and elemental
concentration data and accounts for the seasonal effect
due to differences in atmospheric dispersion conditions.
This approach evidences seasonal differences in the
emission strength of some sources (such as wind-blown
mineral dust) and singles out the presence of sources
active only during one season (i.e. domestic heating).
It also highlights the role of some physico-chemical
processes of secondary aerosol production (i.e. the
increase of secondary sulphates during the summer
when the photochemical activity is highest and the
prevailing aerosol particle phase in secondary organic
compounds during winter).
The observed seasonal behaviour of PM mass
concentration has mainly to be ascribed to differences
in the average atmospheric dispersion registered between
the winter semester and the summer period (it explains
72% and 80% of the PM1 and PM2.5 mass difference in
the two seasons). The seasonal effect is also due to the
presence of an additional emission source (i.e. domestic
heating) active during the cold season; this source
contributes to primary particulate matter as well as to
secondary aerosol production because of its large
emission of gaseous precursors.
The high concentration of sulphates, secondary
organic compounds and, likely, nitrates indicate that
in Milan and in the surrounding area a large contribu-
tion to PM2.5 and PM1 mass is due to secondary
aerosol production. This is favoured by large emissions
of gaseous precursors in the municipality (as well as in
the Lombardy region) and by low mixing layer heights
observed during the winter in the Po valley which
allow the accumulation of secondary aerosol precursor
concentrations.
Acknowledgements
The authors thank the Italian Ministry of Education,
University and Research for the financial support of
this work in the frame of a wider research project
(COFIN2001).
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