Microchemical Journal 80 (2005) 9 17 www.elsevier.

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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, Dar o Go meza
a

Comisio n Nacional de Energ a Ato mica, Unidad de Actividad Qu mica, Centro Ato mico Constituyentes, Av. Gral. Paz 1499, B1650KNA-San Mart n, Pcia. de Buenos Aires, Argentina b Comisio n Nacional de Energ a Ato mica, Unidad de Actividad Combustibles Nucleares, Centro Ato mico Constituyentes, Av. Gral. Paz 1499, B1650KNA-San Mart n, 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 m3 (equivalent to 0.42 Ag g1) for Cd to 1.9 Ag m3 (equivalent to 29.7 mg g1) 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 1:106, 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 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 corresponding 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

areas is exposed to metals and metalloids in suspended 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)

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P. Smichowski et al. / Microchemical Journal 80 (2005) 917 Table 1 Instrumental characteristics and settings for ICP OES Instrument Forward rf power Frequency of rf generator Coolant gas flow rate Auxiliary gas flow rate Sample gas flow rate Solution delivery Automatic sampler Nebulizer Polycrhomator Detector Measurement mode Signal processing mode Background correction Wavelengths (nm) Perkin-Elmer Optima 3100 XL 1300 W 40 MHz (axial view) 15 l min1 0.5 l min1 0.8 l min1 1.0 ml min1 Perkin-Elmer AS90 Cross-flow with Scott type expansion chamber Echelle grating, cross-dispersed, wavelength range (nm): 165403 Segmented-array charge coupled device Continuous nebulization 3 pixels peak area 2 points 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

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 composition 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 Promocio n Cient fica y Tecnolo gica (Agency for Scientific and Technological Development) of Argentina aimed to quantifying metals and metalloids in urban SPM as well as identifying their sources.

Welding Ar from Indura (Buenos Aires, Argentina) was used for ICP OES determinations. Deionized distilled water (DDW) was produced by a commercial mixed-bed ionexchange 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 l1 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 Microscopy (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

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.

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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 min1 and the average total sampling time was 24 h to achieve a concentration of trace metals sufficient for their quantification. 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

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 spectrometry (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 multielemental in nature and possess high sensitivity and appropriate detection power. For ICP OES determinations, multielemental calibrants were prepared from 1000 Ag l1 standard solutions of the individual elements in 0.1 mol l1 HCl. Calibration curves were obtained with matrix-matched calibration standards.

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P. Smichowski et al. / Microchemical Journal 80 (2005) 917 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 spiked with the elements under study Element Al As Cd Cr Cu Fe Mn Ni Pb Ti V Zn Certified 3.42F0.11% 115F10 Ag g1 75F7 Ag g1 403F12 Ag g1 609F27 Ag g1 3.91F0.10% 786F17 Ag g1 82F3 Ag g1 0.655F0.008% (0.40%) 127F7 Ag g1 0.476F0.014% Founda 3.37F0.15% 109F6 Ag g1 70F5 Ag g1 350F29 Ag g1 618F31 Ag g1 3.88F0.15% 780F24 Ag g1 86F6 Ag g1 0.630F0.05% 0.31F0.05% 119F9 Ag g1 0.466F0.020% Recovery test (%) recovery 88 92 85 83 87 89 91 86 90 90 87 85

2.5. Blanks, detection limits and precision Filters used to collect aerosol samples are not free from metals. The concentration of trace metals was also measured by ICP OES in solutions of filters that were treated as the filters loaded with particles to establish a baseline. The blank was a reagent+beaker+filter blank and the concentrations of metals and metalloids measured were subtracted to the ICP OES measurements of real samples. These average concentrations were: Al, 0.72 mg l1 (equivalent to 13 ng m3); Cu, 0.11 mg l1 (equivalent to 2 ng m3); Fe, 2.69 mg l1 (equivalent to 47 ng m3). Using optimized conditions, analytical figures of merit, including detection limit and precision of replicate measurements, were established. Detection limit was calculated following the IUPAC rules on the basis of 3r criterion for 10 replicated measurements of the blank signal. Limits of 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 complexity of the matrix analyzed. 2.6. Validation of measurements of trace elements Table 3 summarizes the concentration of the analytes in the Certified reference material NIST 1648 (Urban particulate matter) as determined by ICP OES. The overall picture can be considered satisfactory, especially if we considered the complexity of the matrix analyzed. To obtain some information about the good performance of the extraction process, the completeness of sample dissolution and the effective control of contamination, absorption or losses, a recovery test was also performed. A multielemental standard was prepared and added to two blank filters. Then, the filters were dried and treated following the recommended procedure. Each one was spiked with the following amounts of analytes (Ag): Al, 1250; As, 2.5; Cd, 0.5; Cr, 2.5; Cu, 12,5; Fe, 1250; Mn, 50; Ni, 12.5; Pb, 250; Sb, 12.5; Ti, 12.5; V, 6.25 and Zn, 250.

Data enclosed in parentheses are noncertified values. a Two sets of replicates, each set consisting of 10 measurements.

Recovery data ranged between 83% (for Cr) and 92% (for As) as shown in Table 4. The good results of the recovery test were also used for quality control of the investigation carried out.

3. Results and discussion Determination of metals and metalloids deposited on glass fiber filters is usually carried out by subsampling the filter, e.g., cutting a small disc from the middle or taking different aliquots of the entire surface. However, different studies performed on aerosols collected by means of highvolume samplers encountered nonhomogeneous depositions of the airborne particles [24,25]. In addition, differences between the specific weights of the various parts of the filters were observed [14]. A nonhomogeneous deposition would cause errors in the calculation of atmospheric concentration of metals. For this reason, we processed the entire filter. It is known that silica, when present at high concentrations, precipitates to form undissolved polysilicic acid [2628]. We observed a precipitate in few digested samples after some days. For this reason, it was necessary to filtrate them again using syringe cellulose ester filters of 0.45 Am pore size. The precipitate was analyzed by SEM, EDAX and XRD and the presence of amorphous Si was confirmed. No other elements were detected. 3.1. Metal and metalloids content in airborne particulate matter Table 4 shows the concentrations in ng m3 of the elements evaluated. A wide range of concentration can be observed with Cd (0.03 ng m3) being the element that exhibits the lowest concentration and Fe (1.9 Ag m3) the highest. The guideline values recommended by the World

Table 2 Limits of detection (LOD) of ICP OES measurements after pretreatment of filter loaded with particulate matter Element Al As Cd Cr Cu Fe Mn Ni Pb Ti V Zn LODs in solution (ng ml1) 9.4 4.3 0.6 9.8 1.8 6.1 1.2 3.0 3.0 5.8 6.5 2.7 LODs in air (ng m3) 0.16 0.07 0.01 0.17 0.03 0.10 0.02 0.05 0.51 0.10 0.11 0.05

P. Smichowski et al. / Microchemical Journal 80 (2005) 917 Table 4 Descriptive statistics of measured concentrations of Campana PM10 Element Minimum Geometric mean Arithmetic mean Maximum WHO Guidelines [34] Time-weighted average Al As Cd Cr Cu Fe Mn Ni Pb Ti V Zn PM10 mass 290.0 0.356 0.030 0.035 0.191 60.7 1.81 0.162 1.41 4.28 0.408 6.13 10.3 829.8 1.580 0.180 1.143 3.103 430.9 16.03 1.094 20.73 11.04 2.194 22.92 39.9 892.6 2.759 0.270 2.833 5.380 552.0 21.23 1.699 70.56 12.39 3.531 36.92 44.4 1384.4 8.032 0.842 17.292 11.571 1872.8 60.83 6.354 838.92 25.44 18.116 130.17 82.1 0.66 5 NAb

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Averaging time lifetimea annual

150 2.5 500 1000

annual lifetimea annual 24 h

All element concentrations are in ng m3. PM10 mass concentration is expressed in Ag m3. 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 1:106. 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 1:106. Total PM10 mass concentration was found to vary from 10.3 to 82.1 Ag m3, with an average value of 44.4 Ag m3. They are lower than 150 Ag m3, 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 m3 and that of Fe ranges between 60.7 and 1872.8 ng m3. 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 m3. 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 m3). 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 correlation matrices and scatter plots of all possible pairs. The pair Fe, Mn shows the highest correlation coefficient (r =0.96), significant at p b104. 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

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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 : 1

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 preliminary results of a recent study [35]. Results are

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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 production 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 emissions 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 m3). 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].

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 significance 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  n u1 X xij xik 2 t 2 CODjk : n i1 xij xik In this case, x ij represents the measured concentration in ng m3 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 selfnormalizing; 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 calculation: (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

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.

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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 baseday 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 m3) 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 1:106, 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

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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, particularly 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 Promocio n Cient fica y Tecnolo gica 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 He ctor Laspina for his kind cooperation in sample treatment.

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