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A particulate matter (PM) source apportionment study was carried out in one of the most polluted districts of Tuscany (Italy), close to an old waste incinerator plant. Due to the high PM10 levels, an extensive field campaign was supported by the Regional Government to identify the main PM sources and quantify their contributions. PM10 daily samples were collected for one year and analysed by different techniques to obtain a complete chemical characterisation (elements, ions and carbon fractions). Hourly fine (2.5 μm) and coarse (2.5-10 μm) aerosol samples were collected by a Streaker sampler for a shorter period and hourly elemental concentrations were obtained by PIXE. Positive Matrix Factorization (PMF) analysis of daily and hourly data allowed the identification of 10 main sources: six anthropogenic (Biomass Burning, Traffic, Secondary Nitrates, Secondary Sulphates, Incinerator, Heavy Oil combustion), two natural (Saharan Dust and Fresh Sea Salt) and two mixed sources (Local Dust and Aged Sea Salt). Biomass burning turned out to be the main source of PM, accounting for 30% of the PM10 mass as annual average, followed by Traffic (18%) and Secondary Nitrates (14%). Emissions from the Incinerator turned out to be only 2% of PM10 mass on average. PM10 composition and source apportionment have been assessed in a polluted area near a waste incinerator, by PMF analysis on daily and hourly compositional data sets.

While more and more studies are being conducted on carbonaceous fractions—organic carbon (OC) and elemental carbon (EC)—in urban areas, there are still too few studies about these species and their effects in polar areas due to their very low concentrations, further, studies in the literature report only data from intensive campaigns, limited in time. We present here for the first time EC–OC concentration long-time data records from the sea-level sampling site of Ny-Ålesund, in the High Arctic (5 years), and from Dome C, in the East Antarctic Plateau (1 year). Regarding the Arctic, the median (and the interquartile range (IQR)) mass concentrations for the years 2011–2015 are 352 (IQR 283–475) ng/m3 for OC and 4.8 (IQR: 4.6–17.4) ng/m3 for EC, which is responsible for only 3% of total carbon (TC). From both the concentration data sets and the variation of the average monthly concentrations, the influence of the Arctic haze on EC and OC concentrations is evident. Summer may be interesting owing to high concentration episodes mainly due to long-range transport (e.g., from wide wildfires in the Northern Hemisphere, as happened in 2015). The average ratio of EC/OC for the summer period is 0.05, ranging from 0.02 to 0.10, and indicates a clean environment with prevailing biogenic (or biomass burning) sources, as well as aged, highly oxidized aerosol from long-range transport. Contribution from ship emission is not evident, but this result may be due to the sampling time resolution. In Antarctica, a 1 year-around data set from December 2016 to February 2018 is shown, which does not present a clear seasonal trend. The OC median (and IQR) value is 78 (64–106) ng/m3, for EC, it is 0.9 (0.6–2.4) ng/m3, weighing for 3% on TC values. The EC/OC ratio mean value is 0.20, with a range of 0.06–0.35. Due to the low EC and OC concentrations in polar areas, correction for the blank is far more important than in campaigns carried out in other regions, largely affecting uncertainties in measured concentrations. Through the years, we have thus developed a new sampling strategy that is presented here for the first time: samplers were modified in order to collect a larger amount of particulates on a small surface, enhancing the capability of the analytical method since the thermo-optical analyzer is sensitive to carbonaceous aerosol areal density. Further, we have recently coupled such modified samplers with a sampling strategy that makes a more reliable blank correction of every single sample possible.

An extensive field campaign was carried out in Florence (Tuscany) to investigate the PM2.5 composition and to identify its sources. The scientific objective of this study is providing a reliable source apportionment, which is mandatory for the application of effective mitigation actions. Particulate matter (PM) was collected for one year, simultaneously in a traffic site, in an urban background, and in a regional background site. While the use of two filter types (quartz and Teflon) allowed obtaining a comprehensive chemical characterization (elemental and organic carbon, ions, elements) by the application of different analytical techniques, the location of the three sampling sites allowed getting a better separation among local, urban, regional and transboundary sources. During shorter periods, the aerosol was also collected by means of a streaker sampler and PIXE (Particle Induced X-ray Emission) analysis of these samples allowed the assessment of hourly resolution elemental time trends. Positive matrix factorisation (PMF) identified seven main sources: traffic, biomass burning, secondary sulphate, secondary nitrates, urban dust, Saharan dust and marine aerosol. Traffic mass concentration contributions were found to be strong only at the traffic site (~8 &mu, g&middot, m&minus, 3, 33% of PM2.5). Biomass burning turned out to be an important PM2.5 source in Florence (~4 &mu, 3), with very similar weights in both city sites while at the regional background site its weight was negligible. Secondary sulphate is an important PM2.5 source on a regional scale, with comparable values in all three sites (~3.5 &mu, 3). On average, the contribution of the &ldquo, natural&rdquo, components (e.g., mineral dust and marine aerosols) to PM2.5 is moderate (~1 &mu, 3) except during Saharan dust intrusions where this contribution is higher (detected simultaneously in all three sites). High-time resolution data confirmed and reinforced these results.

At the 3 MV Tandetron accelerator of the LABEC laboratory of INFN (Florence, Italy) an external beam facility is fully dedicated to PIXE-PIGE measurements of the elemental composition of atmospheric aerosols. All the elements with Z > 10 are simultaneously detected by PIXE typically in one minute. This setup allows us an easy automatic positioning, changing and scanning of samples collected by different kinds of devices: long series of daily PM (Particulate Matter) samples can be analysed in short times, as well as size-segregated and high time-resolution aerosol samples. Thanks to the capability of detecting all the crustal elements, PIXE-PIGE analyses are unrivalled in the study of mineral dust: consequently, they are very effective in the study of natural aerosols, like, for example, Saharan dust intrusions. Among the detectable elements there are also important markers of anthropogenic sources, which allow effective source apportionment studies in polluted urban environments using a multivariate method like Positive Matrix Factorization (PMF). Examples regarding recent monitoring campaigns, performed in urban and remote areas, both daily and with high time resolution (hourly samples), as well as with size selection, are presented. The importance of the combined use of the Particle Induced Gamma Ray emission technique (PIGE) and of other complementary (non-nuclear) techniques is highlighted.

The quantification of the elemental concentration of ambient particulate matter is a challenging task because the observed elemental loadings are not well above the detection limit for most analytical techniques. Although non-destructive nuclear techniques are widely used for the chemical characterization of ambient aerosol, only one multi-element standard reference filter material that mimics ambient aerosol composition has become recently available in the market. To ensure accuracy, reliability and comparability of instruments performance, multiple reference materials with different elemental mass loadings are necessary. In this study, an intercomparison exercise was performed to evaluate the measurement uncertainty and instruments performance using multi-element dust standard reference samples deposited on PTFE filters. The filter samples, produced by means of dust dispersion, were tested in terms of homogeneity, reproducibility and long-term stability (≈40 months). Eight laboratories participated in the exercise. The evaluation of the results reported by the participants was performed by using two sets of reference values: a) the concentrations reported by the Expert Laboratory, b) the robust average concentrations reported by all participants. Most of the reported on the certificate of analysis elements were efficiently detected in the sample loadings prepared as representative for atmospheric samples by the Expert Laboratory. The average absolute relative difference between the reported and the reference values ranged between 0.1% (Ti) and 33.7% (Cr) (CRM-2584). The participants efficiently detected most of the elements except from the elements with atomic number lower than 16 (i.e. P, Al, Mg). The average absolute percentage difference between the participants results and the assigned value as derived by the expert laboratory was 17.5 ± 18.1% (CRM-2583; Cr, Pb excluded) and 16.7 ± 16.7% (CRM-2584; Cr, P excluded). The average “relative robust standard deviation” of the results reported by all participants was 25.1% (CRM-2583) and 22.8% (CRM-2584).

The present work is a part of a scientific study conducted among several Arab countries in west Asia, under an International Atomic Energy Agency (IAEA) regional technical cooperation project for Arasia region. The project aims at producing for the first time a database of particulate matter (PM) elemental concentrations in the region that will help in future air quality studies in order to identify commonalities and differences in the presence and contribution of fingerprint pollution sources among the Arasia Member States. The first regional campaign was launched simultaneously in Lebanon, Iraq, Jordan, Syria and United Arab Emirates, using a harmonized sampling and analysis protocol of PM 10 and PM 2.5 samples. Different samples, collected between October 2014 and February 2015, from the participating countries, were analyzed by PIXE technique and gravimetric measurements were also carried out. The first results of the study will be discussed in a regional perspective. Our study shows that concentrations of fine aerosol fractions are often exceeding the WHO standard values as well as showing some disparities in the obtained values between the different sampling sites. However, some trend similarities of variations with time could also be observed, suggesting a common influence by trans-boundary or external sources of air pollution.

Montale is a small town in Tuscany characterised by high PM10 levels. Close to the town there is a waste incinerator plant. There are many concerns in the population and in the press about the causes of the high levels of pollution in this area. Daily PM10 samples were collected for 1 year by the FAI Hydra Dual sampler and analysed by different techniques in order to obtain a complete chemical speciation (elements by PIXE and ICP-MS, ions by Ion Chromatography, elemental and organic carbon by a thermo-optical instrument); hourly fine ( Positive Matrix Factorization identified and quantified the major aerosol sources. Biomass burning turned out to be the most important source with an average percentage contribution to PM10 of 27% of and even higher percentages during the winter period when there are the highest PM10 concentrations. The contribution of the incinerator source has been estimated as about 6% of PM10.

In the framework of an extensive environmental investigation, promoted by the Italian Health Ministry, the ISPESL (Istituto Superiore per la Prevenzione e la Sicurezza del Lavoro) and the CNR (Consiglio Nazionale della Ricerca), aerosol samples were collected in Taranto (one of the most industrialized towns in southern Italy) with high time resolution and analyzed by PIXE. The samples were collected in two periods (February&ndash, March and June 2004) and in two different sites: an urban district close to the industrial area and a small town 7 km N-NW of Taranto. The use of &lsquo, &lsquo, streaker&rsquo, &rsquo, samplers (by PIXE International Corporation) allowed for the simultaneous collection of the fine (&lt, 2.5 &mu, m) and coarse (2.5&ndash, 10 &mu, m) fractions of particulate matter. PIXE analyses were performed with a 3 MeV proton beam from the 3 MV Tandetron accelerator of the INFN-LABEC laboratory. Particulate emissions as well as their atmospheric transport and dilution processes change within a few hours, but most of the results in literature are limited to daily time resolution of the input samples that are not suitable for tracking these rapid changes. Furthermore, since source apportionment receptor models need a series of samples containing material from the same set of sources in different proportions, a higher variability between samples can be obtained by increasing the temporal resolution rather than with samples integrated over a longer time. In this study, the high time resolution of the adopted approach allowed us to follow in detail the changes in the aerosol elemental composition due to both the time evolution of the industrial emissions and the time changes in meteorological conditions, and thus, transport pathways. Moreover, the location of the sampling sites, along the prevalent wind direction and in opposite positions with respect to the industrial site, allowed us to follow the impact of the industrial plume as a function of wind direction. Positive matrix factorization (PMF) analysis on the elemental hourly concentrations identified eight sources in the fine fraction and six sources in the coarse one.

This study aims to determine the mineral contribution to PM10 in the central Mediterranean Sea, based on 7 yr of daily PM10 samplings made on the island of Lampedusa (35.5° N, 12.6° E). The chemical composition of the PM10 samples was determined by ion chromatography for the main ions, and, on selected samples, by particle-induced X-ray emission (PIXE) for the total content of crustal markers. Aerosol optical depth measurements were carried out in parallel to the PM10 sampling. The average PM10 concentration at Lampedusa over the period June 2004–December 2010 is 31.5 μg m−3, with low interannual variability. The annual means are below the EU annual standard for PM10, but 9.9% of the total number of daily data exceeds the daily threshold value established by the European Commission for PM (50 μg m−3, European Community, EC/30/1999). The Saharan dust contribution to PM10 was derived by calculating the contribution of Al, Si, Fe, Ti, non-sea-salt (nss) Ca, nssNa, and nssK oxides in samples in which PIXE data were available. Cases in which crustal content exceeded the 75th percentile of the crustal oxide content distribution were identified as elevated dust events. Using this threshold, we obtained 175 events. Fifty-five elevated dust events (31.6%) displayed PM10 higher than 50 μg m−3, with dust contributing by 33% on average. The crustal contribution to PM10 has an annual average value of 5.42 μg m−3, and reaches a value as high as 67.9 μg m−3 (corresponding to 49% of PM10) during an intense Saharan dust event. The crustal content estimated from a single tracer, such as Al or Ca, is in good agreement with the one calculated as the sum of the metal oxides. Conversely, larger crustal contents are derived by applying the EU guidelines for demonstration and subtraction of exceedances in PM10 levels due to high background of natural aerosol. The crustal aerosol amount and contribution to PM10 showed a very small seasonal dependence; conversely, the dust columnar burden displays an evident annual cycle, with a strong summer maximum (monthly average aerosol optical depth at 500 nm up to 0.28 in June–August). We found that 71.3% of the dust events identified from optical properties over the atmospheric column display a high dust content at the ground level. Conversely, the remaining 28.7% of cases present a negligible or small impact on the surface aerosol composition due to the transport processes over the Mediterranean Sea, where dust frequently travels above the marine boundary layer, especially in summer. Based on backward trajectories, two regions, one in Algeria–Tunisia, and one in Libya, are identified as main source areas for intense dust episodes occurring mainly in autumn and winter. Data on the bulk composition of mineral aerosol arising from these two source areas are scarce; results on characteristic ratios between elements show somewhat higher values of Ca / Al and (Ca + Mg) / Fe (2.5 ± 1.0, and 4.7 ± 2.0, respectively) for Algeria–Tunisia than for Libyan origin (Ca / Al = 1.9 ± 0.7 and (Ca + Mg) / Fe = 3.3 ± 1.1).

The influence of biomass burning (BB) aerosols, whether of regional or local origin, on fine aerosol levels in the Barcelona urban environment (Spain) was investigated. High-time resolved data on light-absorbing aerosols and inorganic tracers in PM2.5 were combined to this end during a dedicated sampling campaign carried out in winter 2011. The evaluation of PM inorganic components and equivalent black carbon evidenced that local-scale BB emissions were not detectable, whereas a source of K, different to vehicular traffic (road dust) and construction/demolition dust re-suspension, was detectable in the urban area. Source apportionment analysis evidenced the contribution from one source traced by S (62% of the source profile) and K (16% of the source profile), which was interpreted as regional-scale transport of secondary aerosols including BB contributions. The S/K ratio for this source (S/K = 4.4) indicated transport of the polluted air masses, as occurs from the rural areas towards the Barcelona urban environment. On average for the study period, the contribution of K-related aerosols from regional BB to PM2.5 levels in the urban environment was estimated as 1.7 μg/m3 as a daily mean, accounting for 8% of the PM2.5 mass during the winter period under study. The contribution from this source to urban aerosols should be lower on the annual scale., This work was partially funded by the Spanish Ministry of the Environment (MAGRAMA), the Ramón y Cajal Programme and national project CGL2010-19464-CLI. The authors would like to express their gratitude to the ASPB for their interest, as well as for technical and administrative support. The authors gratefully acknowledge the NOAA Air Resources Laboratory (ARL) for the provision of the HYSPLIT transport and dispersion model and/or READY website (http://www.arl.noaa.gov/ready.html) used in this publication.

Hourly-resolved aerosol chemical speciation data can be a highly powerful tool to determine the source origin of atmospheric pollutants in urban environments. Aerosol mass concentrations of seventeen elements (Na, Mg, Al, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Sr and Pb) were obtained by time (1 h) and size (PM2.5 particulate matter < 2.5 μm) resolved aerosol samples analysed by Particle Induced X-ray Emission (PIXE) measurements. In the Marie Curie European Union framework of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies), the approach used is the simultaneous sampling at two monitoring sites in Barcelona (Spain) during September–October 2010: an urban background site (UB) and a street canyon traffic road site (RS). Elements related to primary non-exhaust traffic emission (Fe, Cu), dust resuspension (Ca) and anthropogenic Cl were found enhanced at the RS, whereas industrial related trace metals (Zn, Pb, Mn) were found at higher concentrations at the more ventilated UB site. When receptor modelling was performed with positive matrix factorization (PMF), nine different aerosol sources were identified at both sites: three types of regional aerosols (regional sulphate (S) – 27%, biomass burning (K) – 5%, sea salt (Na-Mg) – 17%), three types of dust aerosols (soil dust (Al-Ti) – 17%, urban crustal dust (Ca) – 6%, and primary traffic non-exhaust brake dust (Fe-Cu) – 7%), and three types of industrial aerosol plumes-like events (shipping oil combustion (V-Ni) – 17%, industrial smelters (Zn-Mn) – 3%, and industrial combustion (Pb-Cl) – 5%, percentages presented are average source contributions to the total elemental mass measured). The validity of the PMF solution of the PIXE data is supported by very good correlations with external single particle mass spectrometry measurements. Some important conclusions can be drawn about the PM2.5 mass fraction simultaneously measured at the UB and RS sites: (1) the regional aerosol sources impact both monitoring sites at similar concentrations regardless their different ventilation conditions; (2) by contrast, local industrial aerosol plumes associated with shipping oil combustion and smelters activities have a higher impact on the more ventilated UB site; (3) a unique source of Pb-Cl (associated with combustion emissions) is found to be the major (82%) source of fine Cl in the urban agglomerate; (4) the mean diurnal variation of PM2.5 primary traffic non-exhaust brake dust (Fe-Cu) suggests that this source is mainly emitted and not resuspended, whereas PM2.5 urban dust (Ca) is found mainly resuspended by both traffic vortex and sea breeze; (5) urban dust (Ca) is found the aerosol source most affected by land wetness, reduced by a factor of eight during rainy days and suggesting that wet roads may be a solution for reducing urban dust concentrations.

Methylene Blue Active Substances (MBAS) and Linear Alkylbenzene Sulphonates (LAS) concentrations, together with organic carbon and ions were measured in atmospheric coastal aerosols in the NW Mediterranean Basin. Previous studies have suggested that the presence of surfactants in coastal aerosols may result in vegetation damage without specifically detecting or quantifying these surfactants. Coastal aerosols were collected at a remote site (Porquerolles Island-Var, France) and at a more anthropised site (San Rossore National Park-Tuscany, Italy). The chemical data were interpreted according to a comprehensive local meteorological analysis aiming to decipher the airborne source and transport processes of these classes of compounds. The LAS concentration (anthropogenic surfactants) was measured in the samples using LC-MS/MS, a specific analytical method. The values were compared with the MBAS concentration, determined by a non-specific analytical method. At Porquerolles, the MBAS concentration (103 ± 93 ng m −3 ) in the summer samples was significantly higher than in the winter samples. In contrast, LAS concentrations were rarely greater than in the blank filters. At San Rossore, the mean annual MBAS concentration (887 ± 473 ng m −3 in PM10) contributed about 10% to the total atmospheric particulate organic matter. LAS mean concentration in these same aerosol samples was 11.5 ± 10.5 ng m −3 . A similar MBAS (529 ± 454 ng m −3 ) – LAS (7.1 ± 4.1 ng m −3 LAS) ratio of ∼75 was measured in the fine (PM2.5) aerosol fraction. No linear correlation was found between MBAS and LAS concentrations. At San Rossore site the variation of LAS concentrations was studied on a daily basis over a year. The LAS concentrations in the coarse fraction (PM10–2.5) were higher during strong sea storm conditions, characterized by strong air flow coming from the sea sector. These events, occurring with more intensity in winter, promoted the formation of primary marine aerosols containing LAS from the sea surface microlayer. In contrast to LAS, MBAS concentrations in the coarse fraction peaked in summer. Therefore, different sources are suggested for the two classes of compounds. In summer, increased MBAS concentration could be an indicator of phytoplanktonic blows enriching the sea surface microlayer with biogenic surfactants. In winter, some spikes in MBAS concentrations in the coarse fraction could be related to LAS concentrations and sea storm events. Moreover, in the fine fraction MBAS have a large concentration maxima in winter, corresponding to air masses coming from polluted continental areas. It is concluded that MBAS concentration in the fine or the coarse fraction is not an appropriate surrogate measurement of LAS concentration in aerosols because of the significant contribution from other sources to the MBAS concentration.

At the 3-MV Tandetron accelerator of LABEC (INFN) an external beam facility is fully dedicated to particle-induced X-ray emission (PIXE) and particle-induced γ-ray emission (PIGE) measurements of atmospheric aerosol elemental composition. All the elements with Z > 10 are simultaneously detected by PIXE in a few minutes and an automatic system for positioning, changing and scanning of the samples allows the analysis of the aerosol collected by different kinds of devices: long series of daily PMX samples can be measured in short times, as well as size-segregated and high time-resolution aerosol samples. Thanks to the capability of detecting all the crustal elements, PIXE-PIGE analyses are unrivalled in the study of mineral dust: as a consequence, they are very effective in the study of natural aerosols, like, for example, mineral dust archived in polar ice cores (for environmental and paleoclimatic studies) and Saharan-dust intrusions. Among the detectable elements, there are also important markers of anthropogenic sources, which allow effective source apportionment studies in polluted urban environments. Examples regarding recent monitoring campaigns, performed in urban and remote areas, both on a daily basis and with high-time resolution (hourly samples), are presented to evidence how PIXE can still provide unique information in aerosol studies or can play a complementary role to X-ray fluorescence or induced coupled plasma mass spectroscopy analysis. Copyright © 2011 John Wiley & Sons, Ltd.

Introduction The concentrations of trace metals, ionic species, and carbonaceous components in PM10 (particulate matter with aerodynamic diameters smaller than 10 µm) were measured from samples collected near an industrial complex, primarily composed of cement plants, in southeastern Spain, from September 2005 to August 2006.

The European AIRUSE LIFE+ project aims at testing existing and future mitigation measures and developing new strategies for the improvement of air quality in Southern European countries. The project involves public and private institutions of Spain, UK, Portugal, Italy and Greece. PM10 and PM2.5 daily samplings have been scheduled for one year (from January 2013) in four urban sites, Barcelona (Spain), Porto (Portugal), Athens (Greece), and Florence (Italy). The daily data set gives an overall representative picture of the PM composition in these urban sites. The project includes also samplings with hourly resolution for limited periods. Hourly samples give an easier identification of the different aerosol sources due to the capability of tracking rapid changes as the ones occurring in many particulate emissions as well as in atmospheric transport and dilution processes. The role of PIXE technique within the project has been described in this paper. The comparison of data obtained by different techniques (e.g. PIXE, IC and ICP) assured a quality assurance control on the huge quantity of data obtained in the project. PIXE data together with those obtained by other analytical techniques have been used to reconstruct the average aerosol chemical composition and in Positive Matrix Factorization (PMF) analysis to determine the aerosol sources and their impact on PM10 and PM2.5 mass. In particular the high sensitivity of PIXE for all the crustal elements (including Si which is not easily detected by ICP) allows the direct determination of the Saharan dust contribution. Finally, the 1-h resolution data, which can be obtained only by PIXE, confirmed and reinforced the identification of the aerosol sources obtained by the daily concentrations.

A multi-analytical approach to chemical analysis of inhalable urban atmospheric particulate matter (PM), integrating particle induced X-ray emission, inductively coupled plasma mass spectrometry/atomic emission spectroscopy, chromatography and thermal-optical transmission methods, allows comparison between hourly (Streaker) and 24-h (High volume sampler) data and consequently improved PM chemical characterization and source identification. In a traffic hot spot monitoring site in Madrid (Spain) the hourly data reveal metallic emissions (Zn, Cu, Cr, Fe) and resuspended mineral dust (Ca, Al, Si) to be closely associated with traffic flow. These pollutants build up during the day, emphasizing evening rush hour peaks, but decrease (especially their coarser fraction PM 2.5-10 ) after nocturnal road washing. Positive matrix factorization (PMF) analysis of a large Streaker database additionally reveals two other mineral dust components (siliceous and sodic), marine aerosol, and minor, transient events which we attribute to biomass burning (K-rich) and industrial (incinerator?) Zn, Pb plumes. Chemical data on 24-h filters allows the measurement of secondary inorganic compounds and carbon concentrations and offers PMF analysis based on a limited number of samples but using fuller range of trace elements which, in the case of Madrid, identifies the continuing minor presence of a coal combustion source traced by As, Se, Ge and Organic Carbon. This coal component is more evident in the city air after the change to the winter heating season in November. Trace element data also allow use of discrimination diagrams such as V/Rb vs. La/Ce and ternary plots to illustrate variations in atmospheric chemistry (such as the effect of Ce-emissions from catalytic converters), with Madrid being an example of a city with little industrial pollution, recently reduced coal emissions, but serious atmospheric contamination by traffic emissions. © 2012 Elsevier Ltd., This project was financed by the Spanish Ministry of Agriculture, Feeding and Environment ( SERCA-058/PC08/3-18.1 ) and a visiting grant (TM) from the Instituto Nazionale di Fisica Nucleare in Florence. Appendix A

In southern European countries, Saharan dust may episodically produce significant increases of PM10, which may also cause the exceedance of the PM10 daily limit value established by the European Directive (2008/50/EC). The detection with very high sensitivity of all the elements that constitute mineral dust makes PIXE technique a very effective tool to assess the actual impact of these episodes. In this work, a review of long-term series of elemental concentrations obtained by PIXE has been accomplished with the aim of identifying the occurrence of Saharan dust transport episodes over long periods in Tuscany and characterising them in terms of composition and impact on PM concentration, tracing back their contribution to the exceedances of the PM10 limit value. The impact of the different Saharan intrusions on PM10 showed a very high variability. During the most intense episodes (which occurred with a frequency of few times per year) the calculated soil dust concentration reached values as high as 25–30 μg m−3, to be compared with background values of the order of 5 μg m−3. The Saharan dust contribution was decisive to cause the exceedance of the PM10 daily limit value in the 1–2% of the days considered in the present work.

High levels of trace gas (O-3 and CO) and aerosol (BC, fine and coarse particle volumes), as well as high scattering coefficient (Sigma(p)) values, were recorded at the regional GAW-WMO station of Mt. Cimone (CMN, 2165 m a.s.l., Italy) during the period 26-30 August 2007. Analysis of air-mass circulation, aerosol chemical characterization and trace gas and aerosol enhancement ratios (ERs), showed that high O-3 and aerosol levels were likely linked to (i) the transport of anthropogenic pollution from northern Italy, and (ii) the advection of air masses rich in mineral dust and biomass burning (BB) products from North Africa. In particular, during the advection of air masses from North Africa, the CO and aerosol levels (CO: 175 ppbv, BC: 1015 ng/m(3), fine particle volume: 3.00 mu m(3) cm(-3), Sigma(p): 84.5 Mm(-1)) were even higher than during the pollution event (CO: 138 ppbv, BC: 733 ng/m(3), fine particles volume: 1.58 mu m(3) cm(-3), Sigma(p): 44.9 Mm < sup-). Moreover, despite the presence of mineral dust able to affect significantly the O-3 concentration, the analysis of ERs showed that the BB event represented an efficient source of fine aerosol particles (e.g. BC), but also of the O-3 recorded at CMN. In particular, the calculated O-3/CO ERs (0.10-0.17 ppbv/ppbv) were in the range of values found in literature for relatively aged (2-4 days) BB plumes and suggested significant photochemical O-3 production during the air-mass transport. For fine particles and Sigma(p), the calculated ERs was higher in the BB plumes than during the anthropogenic pollution events, stressing the importance of the identified BB event as a source of atmospheric aerosol able to affect the atmospheric radiation budget. These results suggest that episodes of mineral dust mobilization and wildfire emissions over North Africa could significantly influence radiative properties (as deduced from Sigma(p) observations at CMN) and air quality over the Mediterranean basin and northern Italy.

Sub-micron sized particles are of increasing concern owing to their effects on human health and on the environment. Up to now there are still very few studies on PM I (i.e. particulate matter with aerodynamic diameter smaller than 1 mu m) chemical characterisation; the sub-micron sized fraction is not under regulations although it is of interest because it is almost exclusively associated to anthropogenic sources. To perform the first large-scale assessment of sub-micron sized aerosol concentrations, composition and sources, two monitoring campaigns at three urban sites in Italy were carried out during the wintertime and summertime of 2004. Chemical characterisation (elements, soluble ionic fraction, elemental and organic carbon) was carried out on PM1 samples: major contributions were due to organic matter (about 30\% in summer and 50\% in winter) and ammonium sulphate (about 10\% in winter and 40\% in summer). During the cold season, nitrates also contributed up to 30\% in Milan (lower contributions were registered at the other two urban sites). Chemical mass closure was achieved with an unaccounted mass in the range 14-22\%. Positive Matrix Factorisation (PMF) was applied to identify the major submicron sized particles' sources. (c) 2007 Elsevier Ltd. All rights reserved.

A project is in progress to study the environmental problems of Taranto, an industrial town in the South of Italy. Within this framework we studied the atmospheric aerosol composition by means of continuous sampling and PIXE measurements. Particulate matter (PM) was collected simultaneously in two sampling sites during winter and summer 2004 by two streaker samplers, which separate the fine and coarse aerosol modes. Hourly concentrations of elements from Na to Pb were measured at the new 3 MV Tandetron accelerator of the LABEC laboratory of INFN in Florence.

{[1] Atmospheric aerosols in the PM(10) and PM(1) fractions have been sampled at the Global Atmospheric Watch station Mount Cimone, Italy ( 2165 m above mean sea level) for 3 months during summer 2004, and simultaneous size distributions have been derived by means of an optical particle counter. Samples have been analyzed by X-ray fluorescence, ion chromatography, and thermal-optical methodology in order to quantify their elemental, ionic, and carbonaceous constituents. The concentration of PM10 was 16.1 +/- 9.8 mu g m(-)3 ( average and standard deviation). Source apportionment allowed us to identify, quantify and characterize the following aerosol classes: anthropogenic pollution ( 10 mu g m(-3)), mineral dust ( 4 mu g m(-3)), and sea salt ( 0.2 mu g m(-3)). Pollution has been further split into ammonium sulfate (44\%), organic matter (42\%), and other compounds (14\%). The nitrate/sulfate ratio in the polluted aerosol was 0.1. Fine particles have been completely related to the polluted aerosol component, and they represented 70\% in weight of pollution. Coarse particles characterized the dust and salt components, and crustal oxides have been found to be the largest responsible for the aerosol concentration variations that occurred during the campaign. Nitrate has also been found in the coarse particles, representing similar to 10\% of mineral dust. The analysis of the transport mechanisms responsible for aerosol fluctuations permitted us to identify the origin of the major aerosol components: Pollution has been ascribed to regional transport driven by boundary layer meteorology, whereas mineral dust has been related to long-range transport events originating in the Sahara and Sahel. A particularly significant Saharan episode has been identified on 10 August 2004 ( PM(10) daily concentration, 69.9 mu g m(-3)). Average elemental ratios for the African dust events were as follows: Si/Al = 2.31, Fe/Ca = 0.94, Ca/Al = 0.90, K/Ca = 0.44, Ti/Ca = 0.11, and Ti/Fe = 0.12.}

A set of PM 2.5 samples ( n = 121) collected at an urban background location in Elche (in southeastern Spain) from December 2004 to November 2005 was analysed by particle-induced X-ray emission (PIXE) and ion chromatography in order to provide source identification and potential source locations. Positive matrix factorization (PMF) was used to estimate source profiles and their mass contributions. The PMF modelling identified six sources: aged sea salt (9.2%), ammonium sulphate (40.4%), soil dust related to Saharan outbreaks (13.0%), traffic 1 (18.9%), nitrate aerosol and traffic 2 (5.5%) and local soil dust (6.0%). Potential source contribution function (PSCF) was then used to identify potential source locations. Scarce influence from Mediterranean and European regions was found with the exception of the nitrate source, whose potential source areas were northern Italy and eastern France. Primary source regions for the remaining components (ammonium sulphate, soil dust-related to Saharan outbreaks and aged sea salt) with known mass contributions due to long-range transport have a marked Atlantic and North African location, primarily between Morocco and northwestern Algeria. DOI: 10.1111/j.1600-0889.2010.00510.x