Microchemical Journal 80 (2005) 9 17

www.elsevier.com/locate/microc

Inductively coupled plasma optical emission spectrometric determination

of trace element in PM10 airborne particulate matter collected
in an industrial area of Argentina
Patricia Smichowskia,*, Julieta Marrerob, Daro Gomeza
a
Comision Nacional de Energa Atomica, Unidad de Actividad Qumica, Centro Atomico Constituyentes, Av. Gral. Paz 1499,
B1650KNA-San Martn, Pcia. de Buenos Aires, Argentina
b
Comision Nacional de Energa Atomica, Unidad de Actividad Combustibles Nucleares, Centro Atomico Constituyentes,
Av. Gral. Paz 1499, B1650KNA-San Martn, Pcia. de Buenos Aires, Argentina

Received 12 July 2004; accepted 29 July 2004

Abstract

Trace metals of relevance from the environmental and toxicological point of view were quantified in the city of Campana, Buenos
Aires, Argentina. The collection of particulate matter was performed on ash-free fiber glass filters using high-volume samplers with a
PM10 sampling head, during a 3-month period in 2002. An acid leaching of elements deposited on the filters was adopted paying special
attention to the recovery of volatile elements. Analysis was performed by inductively coupled plasma optical emission spectrometry (ICP
OES) to ascertain the concentrations of 12 key elements, namely, Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn. The validation of the
procedure was performed by the analysis of the standard reference material NIST 1648, urban particulate matter, and good agreement
between concentrations found and the reported certified values was achieved. Blank filters were spiked with the analytes investigated and
the recoveries varied between 83% and 92%. Metal concentrations spanned the range 0.03 ng m
3 (equivalent to 0.42 Ag g
1) for Cd to
1.9 Ag m
3 (equivalent to 29.7 mg g
1) for Fe. The results obtained show that the pollutants of special environmental and health concern
are As and Pb. Mean As concentration was higher than the guideline value associated with an excess cancer risk of 1:10
6, reported by
the World Health Organization (WHO). Lead is the only element that showed higher concentrations than those recently measured in the
large and heavily trafficked metropolitan area of Buenos Aires. CadmiumNPbNAsNZnNCu are the elements more enriched in airborne
PM10.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Airborne particulate matter; Trace elements; Inductively coupled plasma optical emission spectrometry; Enrichment factors

1. Introduction areas is exposed to metals and metalloids in suspended

At present, there is a growing interest for the evaluation
of the environmental impact associated with industrial
activity that demands the implementation of studies
conducted to assess the current influence of the correspond-
ing emission sources. Population in the vicinity of industrial
* Corresponding author. Tel.: +54 11 6772 7873; fax: +54 11 6772
7886.
E-mail address: smichows@cnea.gov.ar (P. Smichowski).
0026-265X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2004.07.023
particles, which are often well above natural background
levels. The release of these elements, contained in airborne
particulate matter, can eventually affect human health since
they can be absorbed into lung tissues during breathing. The
nature and magnitude of this hazard in a given situation
depend on a complex combination of many factors,
including particle size distribution, wind-speed range,
airborne concentration, particle morphology, mineralogy
and chemical composition [1].
High-volume samplers using glass fiber filters have
been widely used for suspended particulate matter (SPM)
10 P. Smichowski et al. / Microchemical Journal 80 (2005) 917
collection in a number of contaminated areas [24]
because of their high collection efficiency for particulates
and low resistance [5] even when they may contain
relatively high levels of some trace elements as impurities
[6].
Different digestion procedures (ashing, acid leaching,
microwave digestion) and analysis schemes for the
determination of trace elements in environmental samples
were reported, [79] but much less on digestion of real
world atmospheric aerosol. In this study, we adopted to
extract metals from filters with aqua regia following a
procedure similar to that successfully used in a previous
work [10].
The application of inductively coupled plasma-based
techniques to air quality monitoring is now widespread
[1,1014]. These techniques can be applied to all possible
matrices and analytes and are characterized by extended
dynamic concentration ranges (several orders of magnitude),
are multielemental in nature and possess high sensitivity and
appropriate detection power.
In Argentina, studies concerning the chemical composi-
tion of PM10 have been mainly focused on the city of
Buenos Aires [1519] and only few investigations have
been conducted in industrial cities along the territory where
higher levels of metals could be expected [20, 21]. In this
context, a study was planned to ascertain the level of metal
and metalloids in airborne particles in the industrial city of
Campana (34810VS, 58855VW), where one of the three
largest industrial complexes along the Parana River corridor
is located. In addition to the large stationary sources, the
city receives the influence of mobile sources, such as
vehicular traffic. The elements evaluated, namely, Al, As,
Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn were quantified by
inductively coupled plasma optical emission spectrometry
(ICP OES) after extraction of metals from the filters.
Enrichment factors were assessed to get information of
potential contribution of anthropogenic sources and were
calculated using the average crustal profile as a reference
[22].
This study is part of a national project funded by the
Agencia de Promocion Cientfica y Tecnologica (Agency
for Scientific and Technological Development) of Argentina
aimed to quantifying metals and metalloids in urban SPM as
well as identifying their sources.
2. Experimental
2.1. Instrumentation and reagents
A Perkin-Elmer (Norwalk, CT, USA) ICP Optima 3100
XL (axial view) simultaneous inductively coupled Ar
plasma optical emission spectrometer provided with a
Model AS 90 autosampler was used for trace elements
determination. Instrumental details and operating conditions
are summarized in Table 1.
Table 1
Instrumental characteristics and settings for ICP OES
Instrument Perkin-Elmer Optima 3100 XL
Forward rf power 1300 W
Frequency of rf generator 40 MHz (axial view)
Coolant gas flow rate 15 l min
1
Auxiliary gas flow rate 0.5 l min
1
Sample gas flow rate 0.8 l min
1
Solution delivery 1.0 ml min
1
Automatic sampler Perkin-Elmer AS90
Nebulizer Cross-flow with Scott type
expansion chamber
Polycrhomator Echelle grating, cross-dispersed,
wavelength range (nm): 165403
Detector Segmented-array charge coupled device
Measurement mode Continuous nebulization
Signal processing mode 3 pixels peak area
Background correction 2 points
Wavelengths (nm) As, 188.979; Al, 308.215; Cd, 228.802;
Cr, 267.716; Cu, 324.742; Fe, 238.204;
Mn, 257.610; Ni, 232.003; Pb, 217.000;
Sb, 206.836; Ti, 337.279; V, 290.880;
Zn, 206.200
Welding Ar from Indura (Buenos Aires, Argentina) was
used for ICP OES determinations. Deionized distilled water
(DDW) was produced by a commercial mixed-bed ion-
exchange system Barnstead (Dubuque, IA, USA) fed with
distilled water. All reagents were of analytical grade.
Hydrochloric and nitric acids (Merck, Darmstadt, Germany)
were used for sample treatment and preparation of the
standards. Commercially available 1000 mg l
1 standard
solutions (Merck) of the elements analyzed were used.
Diluted working solutions were prepared daily by serial
dilutions of those stock solutions. All samples and standards
were stored in polyethylene bottles (50 ml) or FalconR
tubes.
The morphology of the insoluble residue that appeared in
some filtrates was inspected by Scanning Electron Micro-
scopy (SEM) on a Philips 515 instrument. Compositional
identification of the insoluble residue was performed by
Energy Dispersive X-ray Analysis on a Philips 515 scanning
electron microscope. All spectra were obtained at 1020 kV
in a 50-s analysis time.
2.2. Sample collection
Levels of metals and metalloids in suspended particles
were studied in a key monitoring site in the city of
Campana, Buenos Aires province, Argentina. The city is
located at 75 km NW of the city of Buenos Aires on the
right margin of the Parana River (Fig. 1a). The city has a
population of about 90,000 inhabitants and holds a
considerable industrial activity that includes two oil
refineries, an integrated steel mill and several industrial
facilities that are distributed in a pincer-like manner
embracing the urban area. The industrial zone is located
on the sedimentary terrain between the shore of the river and
 P. Smichowski et al. / Microchemical Journal 80 (2005) 917
Fig. 1. (a) Geographical location of the city of Campana, Argentina; (b) layout of the city of Campana indicating the location of the monitoring site.
its original 20 m high bank cliffs. The urban area is on the
upland delimited by the edge of the bank.
Thirty-three samples were collected during a 45-day
measuring campaign done in the Southern Hemispheres
wintertime. The monitoring site was located on the edge of
the urban area, 800 m from the center of the city and
overlooking the industrial zone. Because of its key location,
this site is normally considered by the local environmental
authorities as representative of the air pollution relative to
the industrial activity of the area under study.
Airborne particulate matter samples were collected on
ash-free fiber glass filters (810 in., ADVANTEC, GB100R,
0.6 Am nominal rating) for 45 days with a high-volume air
sample (SIBATA, HV 1000F) with a PM10 sampling head.
The sampling flow rate used was 1000 l min
1 and the
average total sampling time was 24 h to achieve a
concentration of trace metals sufficient for their quantifica-
tion. The average air volume collected daily was 1440 m3.
Each filter was placed in a clean polyethylene bag during
transport and storage. The glass fiber filters were heated in a
vacuum drying oven at 110120 8C during 120 min prior to
use. The filters were weighed (after moisture equilibration)
before and after sampling to determine the net particulate
mass gain. Filter conditioning environment during the 24-h
equilibration period included controlled temperature with
less than F3 8C and constant relative humidity within F5%.
Operation, treatment and handling of samples and data
validation were carried out according to QA/QC guidelines
of the World Health Organization (WHO) [23].
2.3. Sample treatment
Once in the laboratory, filters loaded with airborne
particulate matter (with an active surface of about 500
11
cm2) or blank filter were folded and cut in pieces of about
22 cm. Pieces were carefully placed into a reaction
vessel and 100 ml of aqua regia were added. The vessel
was connected with a reflux condenser and heated on a
hot plate at 100 8C for 2 h and then allowed to cool
slowly at room temperature. Deionized water was added
and the solution was filtrated to remove carbon particles
and taking special attention in extracting all the liquid
contained in the filter material. The residual filter was
washed several times with deionized water. The solution
was evaporated to about 20 ml and transferred into a
volumetric flask and made up to 25 ml with deionized
water. A blank filter was treated following the procedure
described above.
About 250 mg of the certified reference material NIST
SRM 1648 (urban particulate matter) were weighed onto a
blank filter and subject to the same treatment as for the
samples.
2.4. Sample analysis
Inductively coupled plasma optical emission spectrom-
etry (ICP OES) was employed in the determination of
metals and metalloids in airborne particulate matter
collected on glass fiber filters. This technique can be
applied to different matrices after a suitable dissolution
procedure and is characterized by extended dynamic
concentration range (46 orders of magnitude), is multi-
elemental in nature and possess high sensitivity and
appropriate detection power.
For ICP OES determinations, multielemental calibrants
were prepared from 1000 Ag l
1 standard solutions of the
individual elements in 0.1 mol l
1 HCl. Calibration curves
were obtained with matrix-matched calibration standards.
12 P. Smichowski et al. / Microchemical Journal 80 (2005) 917

2.5. Blanks, detection limits and precision Table 3

Results obtained in the analysis of the standard reference material NIST
1648 (Urban particulate matter) by ICP OES and recovery test of blank
Filters used to collect aerosol samples are not free from filters spiked with the elements under study
metals. The concentration of trace metals was also measured
Element Certified Founda Recovery test
by ICP OES in solutions of filters that were treated as the (%) recovery
filters loaded with particles to establish a baseline. The
Al 3.42F0.11% 3.37F0.15% 88
blank was a reagent+beaker+filter blank and the concen- As 115F10 Ag g
1 109F6 Ag g
1 92
trations of metals and metalloids measured were subtracted Cd 75F7 Ag g
1 70F5 Ag g
1 85
to the ICP OES measurements of real samples. These Cr 403F12 Ag g
1 350F29 Ag g
1 83
average concentrations were: Al, 0.72 mg l
1 (equivalent to Cu 609F27 Ag g
1 618F31 Ag g
1 87
Fe 3.91F0.10% 3.88F0.15% 89
13 ng m
3); Cu, 0.11 mg l
1 (equivalent to 2 ng m
3); Fe,
Mn 786F17 Ag g
1 780F24 Ag g
1 91
2.69 mg l
1 (equivalent to 47 ng m
3). Ni 82F3 Ag g
1 86F6 Ag g
1 86
Using optimized conditions, analytical figures of merit, Pb 0.655F0.008% 0.630F0.05% 90
including detection limit and precision of replicate measure- Ti (0.40%) 0.31F0.05% 90
ments, were established. Detection limit was calculated V 127F7 Ag g
1 119F9 Ag g
1 87
Zn 0.476F0.014% 0.466F0.020% 85
following the IUPAC rules on the basis of 3r criterion for
10 replicated measurements of the blank signal. Limits of Data enclosed in parentheses are noncertified values.
a
Two sets of replicates, each set consisting of 10 measurements.
detection in solution and in air are set forth in Table 2. The
RSDs for the 12 elements evaluated are in general in a more
than satisfactory interval (3.011.1%) considering the Recovery data ranged between 83% (for Cr) and 92% (for
complexity of the matrix analyzed. As) as shown in Table 4. The good results of the recovery
test were also used for quality control of the investigation
2.6. Validation of measurements of trace elements carried out.

Table 3 summarizes the concentration of the analytes in

the Certified reference material NIST 1648 (Urban partic- 3. Results and discussion
ulate matter) as determined by ICP OES. The overall picture
can be considered satisfactory, especially if we considered Determination of metals and metalloids deposited on
the complexity of the matrix analyzed. glass fiber filters is usually carried out by subsampling the
To obtain some information about the good performance filter, e.g., cutting a small disc from the middle or taking
of the extraction process, the completeness of sample different aliquots of the entire surface. However, different
dissolution and the effective control of contamination, studies performed on aerosols collected by means of high-
absorption or losses, a recovery test was also performed. volume samplers encountered nonhomogeneous depositions
A multielemental standard was prepared and added to two of the airborne particles [24,25]. In addition, differences
blank filters. Then, the filters were dried and treated between the specific weights of the various parts of the
following the recommended procedure. Each one was filters were observed [14]. A nonhomogeneous deposition
spiked with the following amounts of analytes (Ag): Al, would cause errors in the calculation of atmospheric
1250; As, 2.5; Cd, 0.5; Cr, 2.5; Cu, 12,5; Fe, 1250; Mn, 50; concentration of metals. For this reason, we processed the
Ni, 12.5; Pb, 250; Sb, 12.5; Ti, 12.5; V, 6.25 and Zn, 250. entire filter.
It is known that silica, when present at high concen-
trations, precipitates to form undissolved polysilicic acid
Table 2 [2628]. We observed a precipitate in few digested samples
Limits of detection (LOD) of ICP OES measurements after pretreatment of
filter loaded with particulate matter
after some days. For this reason, it was necessary to filtrate
them again using syringe cellulose ester filters of 0.45 Am
Element LODs in LODs in
solution (ng ml
1) air (ng m
3)
pore size. The precipitate was analyzed by SEM, EDAX and
XRD and the presence of amorphous Si was confirmed. No
Al 9.4 0.16
As 4.3 0.07 other elements were detected.
Cd 0.6 0.01
Cr 9.8 0.17 3.1. Metal and metalloids content in airborne particulate
Cu 1.8 0.03 matter
Fe 6.1 0.10
Mn 1.2 0.02
Ni 3.0 0.05 Table 4 shows the concentrations in ng m
3 of the
Pb 3.0 0.51 elements evaluated. A wide range of concentration can be
Ti 5.8 0.10 observed with Cd (0.03 ng m
3) being the element that
V 6.5 0.11 exhibits the lowest concentration and Fe (1.9 Ag m
3) the
Zn 2.7 0.05
highest. The guideline values recommended by the World
 P. Smichowski et al. / Microchemical Journal 80 (2005) 917 13

Table 4
Descriptive statistics of measured concentrations of Campana PM10
Element Minimum Geometric mean Arithmetic mean Maximum WHO Guidelines [34]
Time-weighted Averaging
average time
Al 290.0 829.8 892.6 1384.4
As 0.356 1.580 2.759 8.032 0.66 lifetimea
Cd 0.030 0.180 0.270 0.842 5 annual
Cr 0.035 1.143 2.833 17.292 NAb
Cu 0.191 3.103 5.380 11.571
Fe 60.7 430.9 552.0 1872.8
Mn 1.81 16.03 21.23 60.83 150 annual
Ni 0.162 1.094 1.699 6.354 2.5 lifetimea
Pb 1.41 20.73 70.56 838.92 500 annual
Ti 4.28 11.04 12.39 25.44
V 0.408 2.194 3.531 18.116 1000 24 h
Zn 6.13 22.92 36.92 130.17
PM10 mass 10.3 39.9 44.4 82.1
All element concentrations are in ng m
3. PM10 mass concentration is expressed in Ag m
3. Guidelines of the World Health Organization for air pollutants of
special environmental and health significance are informed as a reference.
a
Concentration of carcinogenic air pollutant associated with an excess lifetime cancer risk of 1 per 1,000,000.
b
Carcinogenic risk is related only to the Cr(VI) species.

Health Organization (WHO) [29] for air pollutants of
special environmental and health concern are also shown
in Table 4. These pollutants include those substances with
effects other than cancer, namely, Cd, Mn, Pb and V, and
those with guideline values based on carcinogenic effects,
As and Ni. It can be observed that the concentrations of the
elements of the first group are well below these guideline
values. Average Ni concentration is also below the reported
guideline level associated with an excess lifetime cancer risk
of 1:10
6. Arsenic deserves certain consideration by local
risk managers. Although the average As concentration is
below the range of expected concentrations in cities without
substantial industrial emissions of this element [29], it is
above the reported concentration associated with an excess
lifetime cancer risk of 1:10
6. Total PM10 mass concen-
tration was found to vary from 10.3 to 82.1 Ag m
3, with an
average value of 44.4 Ag m
3. They are lower than 150 Ag
m
3, the present national air quality standard for PM10.
Best fitting distribution for each element concentration
for the entire data set was assessed by means of Quantile
Quantile (QQ) plots [30]. QQ plots were generated
using the STATISTICA software (StatSoft, Tulsa, OK,
USA). The distributions chosen to fit the data were those
that are being used in the context of air pollution, namely,
Beta, Extreme Value, Gamma, Lognormal and Weibull
distributions [31,32]. For most elements, namely, As, Cr,
Fe, Mn, Ni, V and Zn, the two-parameter Lognormal and
Weibull distributions provided equivalent and generally
better approximations of the data. The Extreme Value and
the normal distributions provided a better fit for the Al,
Cu, and Ti concentration data than the Gamma and
Weibull distributions. The PM10 mass concentration was
found to be normally distributed while no satisfactory fit
was found for Pb. In short, the measured concentrations of
all the elements, except Pb, are adequately fitted by right-
skewed distributions. For this reason, both the arithmetic
and the geometric mean are reported in Table 4 since the
last one is a better indication of the central tendency of the
data.
The element concentrations can be grouped in four
ranges (Table 4). The first group is composed by the
geological elements, namely, Al and Fe that show the
highest concentrations. Aluminum concentration ranges
between 290 and 1384.4 ng m
3 and that of Fe ranges
between 60.7 and 1872.8 ng m
3. The second group, Mn,
Pb, Ti and Zn, exhibits relatively lower concentrations being
Pb, the element that varies within the widest range, from
1.41 to 838.9 ng m
3. CopperNVNCrNAs~Ni conform the
third group. Cadmium is the metal with the lowest range of
concentrations of all the elements analyzed (0.030 to 0.842
ng m
3). The standard deviations of the 33 samples
analyzed show a significant dispersion of the measured
concentrations that are consistent with data sets from other
industrial locations in Latin America [33].
Correlations between element concentrations were
explored using the STATISTICA software through correla-
tion matrices and scatter plots of all possible pairs. The pair
Fe, Mn shows the highest correlation coefficient (r=0.96),
significant at pb10
4. These two elements are correlated
with Cr, Pb and Ti with correlation coefficients within the
range 0.810.89. Another significant correlation appears
between Ni and V (r=0.88). Titanium is the only element
whose correlation coefficient with respect to PM10 mass
concentration is higher than 0.7. Fig. 2 gives an overall
picture of the discussed significant correlations.
3.2. Enrichment factors
One approach to characterize the presence of a given
trace element (X) from anthropogenic origin is to calculate
14 P. Smichowski et al. / Microchemical Journal 80 (2005) 917

Fig. 2. Scatter plots of measured concentrations that showed significant correlations; (a) Ti vs. PM10; (b) Cr vs. Fe, Mn vs. Fe, Ti vs. Fe; (c) Ni vs. V.

the so-called denrichment factorT (EF) by employing a
reference element (E). The elements that have EF values
between 1 and 10 are usually termed as crustal, while
elements with EF values in the range 10 to 50,000 are
generally emitted by anthropogenic sources [34].
EFX X =Esample = X =Ecrustal rock :
Three sets of EFs were calculated using Eq. (1) with Al,
Fe and Ti as normalizing elements. Titanium was selected as
the reference element (E) because it exhibited the lowest
enrichment factors among the three reference elements
considered and also because it is the element that is most
homogenously distributed in the local soil, according to the
1 preliminary results of a recent study [35]. Results are
 P. Smichowski et al. / Microchemical Journal 80 (2005) 917
depicted in Fig. 3. Aluminum and Fe, the so-called
geological or crustal elements, exhibit the lowest EF values
(b5). The low EF values of Cr (EF=3.5) and Mn (EF=9.4)
indicate that these elements may not be linked to an
anthropogenic origin in the filters analyzed. Furthermore,
these EF values and the high degree of correlation between
Cr, Fe, Mn and Ti allows to infer that the contribution of
these elements to the PM10 samples analyzed might be
linked to crustal soil dust.
A second group is formed by elements with EF values
between 15 and 200 (V=16.6, Ni=29.2, Cu=99.5 and
Zn=182). Refineries located in the studied city are likely
sources of Ni and V since compounds of these metals are
used in fluid catalytic cracking. The relatively high EF value
of Zn reflects anthropogenic sources since Zn is mostly
emitted from coal combustion, iron and steel production and
waste incineration. Although there is no significant coal
combustion or waste incineration in the area, steel produc-
tion is present.
The highest EF values, within the range 300700,
correspond to the group formed by potentially toxic
elements, namely, As (373), Pb (536) and Cd (662). These
high EF values unambiguously point to an anthropogenic
origin although the measured Cd concentration is relatively
low and that of As is below the range of expected
concentrations in cities without substantial industrial emis-
sions of this element [29]. Arsenic in air is present mainly in
particulate forms as inorganic species. It is known that
emissions of As to air arise mainly from smelting of metals,
fuel combustion and the use of pesticides. These activities
are present in the area where Campana is located and might
be responsible of the concentrations found in PM10
(maximum concentration: 8.032 ng m
3). Lead is a
ubiquitous pollutant in the ecosystem. In this case, both
the EF and the atmospheric concentration are high. As an
example, mean Pb concentration registered in Campana is
about three times higher than that of Buenos Aires [10].
Fig. 3. Enrichment factors for elements in the 33 samples analyzed normalised to Ti.The average continental crust given by Taylor [22] was selected as the
reference profile.
15
Although Pb has traditionally been linked to traffic origin,
the use of unleaded gasoline since 1995 have considerably
reduced atmospheric level of Pb; consequently, the signifi-
cance of Pb sources in the atmosphere is currently changing.
It was reported that the dominant Pb compound in aerosols,
identified as PbSO4d (NH4)2SO4 by XRD [36], has a
secondary origin arising from transformations of the
primary emitted aerosol compounds during atmospheric
transport [37].
3.3. Daily variations of PM10 chemical constituents
Daily variations of the element concentration were
assessed by means of the coefficient of divergence (COD),
defined as follows.
v
u 
u1 X n
xij
xik 2
CODjk t : 2
n i1 xij xik
In this case, x ij represents the measured concentration
in ng m
3 for a chemical component i at day j; and j and
k represent two sampling days. Wongphatarakul et al. [38]
introduced the COD for assessing similarities in chemical
composition between monitoring sites. For our 2-month
sampling campaign, we extended the usage of the COD
for comparing day-to-day variations at the monitoring site.
As it has been pointed out [15], the COD is self-
normalizing; if 2 days are similar in chemical composition,
the COD approaches zero, otherwise, the COD approaches
one.
We considered four sets of elements for CODs calcu-
lation: (1) all measured elements; (2) geological elements
(Al and Fe); (3) minor elements (Mn, Pb, Ti and Zn); (4)
trace elements (As, Cd, Cu, Cr, Ni and V). Since the
campaign involved 36 days, 360 day-to-day CODs were
calculated. Results are depicted in Fig. 4a. The geological
elements are more homogeneously distributed during the
16 P. Smichowski et al. / Microchemical Journal 80 (2005) 917
Fig. 4. (a) Box and whiskers plots of day-to-day CODs distribution; (b) minimum, mean and maximum values of CODs for each monitoring day. CODs of
subsequent days are also indicated.
sampling period than the remaining elements. Minor and
trace elements exhibited similar variations. Persistence of
metal levels in airborne PM10 were explored by comparing
for each sampling day, the COD of its subsequent day with
the CODs of all other days (Fig. 4b). For the most part, the
differences between subsequent days are below the average
differences between the base-day and all other sampling
days. The CODs of 13 out of 30 pairs of subsequent days
were within 20% of the minimum COD value for each base-
day while the CODs of 6 pairs of subsequent days
correspond to the minimum COD value. This seem to
indicate a certain persistence of metal levels that is
frequently altered either by changes in emission patterns
or meteorological conditions.
4. Conclusions
On the basis of the findings of this study, ICP OES
resulted in a fully adequate technique for determining metals
and metalloids in airborne particulate matter collected on
filters.
This paper provides information not only about the
concentration of 12 element constituents of PM10 in the
industrial area of Campana, Argentina but also about their
temporal distribution. Violations of the 24-h PM10 national
standard (150 Ag m
3) were not registered during the
monitoring campaign.
From the pollutant of special environmental and health
concern, As and Pb concentrations in airborne PM10 from
Campana deserve to be considered. Mean As concentration
during the monitoring period was higher than the guideline
value associated with an excess cancer risk of 1:10
6,
reported by the World Health Organization. Lead is the only
element that showed higher concentrations than those
recently measured in the large and heavily trafficked
metropolitan area of Buenos Aires [10]. However, these
Pb levels are lower than the concentrations measured before
the use of unleaded gasoline in Argentina since 1995. The
higher Pb concentration in Campana and its atypical
 P. Smichowski et al. / Microchemical Journal 80 (2005) 917
distribution might be attributed to sources other than traffic
possibly arising from transformations of Pb compounds in
the atmosphere.
The elements that presented values of enrichment factors
that may unambiguously linked to anthropogenic origin
were: CdNPbNAsNZnNCu. Their presence is attributed to the
large stationary sources of local industrial facilities, partic-
ularly the steel mill and the refinery. Arsenic may be also
linked to the use of pesticides in the nearby agricultural
activities.
To closely follow the impact of industrial activities on air
quality of the city of Campana, it is planned to perform the
same type of monitoring studies in the next few years in the
framework of a national project aimed to quantify metals
and metalloids in SPM as well as identifying their sources in
key regions of Argentina.
Acknowledgements
This work is part of CNEA-CAC Project P5-PID 36-2
and 36-4. Financial support was provided by the Agencia
Nacional de Promocion Cientfica y Tecnologica through
Project PICT-2000 N8 13-08772. Carlos Romero (CNEA)
who was in charge of the sampling campaign and Griselda
Polla (CNEA) who performed the XRD and SEM analysis
are also acknowledged. The authors are grateful to Hector
Laspina for his kind cooperation in sample treatment.
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