Hybrid multiple-site mass closure and source apportionment of PM2.5 and aerosol acidity at major cities in the Po Valley.

This study investigates the major chemical components, particle-bound water content, acidity (pH), and major potential sources of PM2.5 in major cities (Belluno, Conegliano, Vicenza, Mestre, Padua, and Rovigo) in the eastern end of the Po Valley. The measured PM2.5 mass was reconstructed using a multiple-site hybrid chemical mass closure approach that also accounts for aerosol inorganic water content (AWC) estimated by the ISORROPIA-II model. Annually, organic matter accounted for 31-45% of the PM2.5 at all sites, followed by nitrate (10-19%), crustal material (10-14%), sulfate (8-10%), ammonium (5-9%), elemental carbon (4-7%), other inorganic ions (3-4%), and trace elements (0.2-0.3%). Water represented 7-10% of measured PM2.5. The ambient aerosol pH varied from 1.5 to 4.5 with lower values in summer (average in all sites 2.2 ± 0.3) and higher in winter (3.9 ± 0.3). Six major PM2.5 sources were quantitatively identified with multiple-site positive matrix factorization: secondary sulfate (34% of PM2.5), secondary nitrate (30%), biomass burning (17%), traffic (11%), re-suspended dust (5%), and fossil fuel combustion (3%). Biomass burning accounted for ~90% of total PAHs. Inorganic aerosol acidity was driven primarily by secondary sulfate, fossil fuel combustion (decreasing pH), secondary nitrate, and biomass burning (increasing pH). Secondary nitrate was the primary driver of the inorganic AWC variability. A concentration-weighted trajectory (multiple-site) analysis was used to identify potential source areas for the various factors and modeled aerosol acidity. Eastern and Central Europe were the main source areas of secondary species. Less acidic aerosol was associated with air masses originating from Northern Europe owing to the elevated presence of the nitrate factor. More acidic particles were observed for air masses traversing the Po Valley and the Mediterranean, possibly due to the higher contributions of fossil fuel combustion factor and the loss of nitric acid due to its interaction with coarse sea-salt particles.

A procedure to evaluate the factors determining the elemental composition of PM2.5. Case study: the Veneto region (northeastern Italy).

The Po Valley is one of the most important hot spots in Europe for air pollution. Morphological features and anthropogenic pressures lead to frequent breaching of air quality standards and to high-pollution episodes in an ~46 × 103-km2-wide alluvial lowland. Therefore, it is increasingly important to study the air quality in a wide geographical scale to better implement possible and successful mitigation measures. The Veneto region lies in the eastern part of the Po Valley and the elemental composition of PM has been mainly studied in the Venice area, whereas scarce data are available for the remaining territory of the region. In this study, the elemental composition of PM2.5 was investigated over 1 year (2012-2013) at six major cities of the Veneto region. Samples were analyzed for 16 elements (Ca, Al, Fe, S, K, Mg, Ti, Mn, Zn, Ba, As, Ni, Pb, Sb, V, and Cu), and results were processed to investigate spatial and seasonal variations, the influence of meteorological factors, and the most probable sources by using a procedure based on (i) elemental ratios (Cu/Sb, Cu/Zn, Cu/Pb, Mn/V, V/Ni, and Zn/Pb), (ii) cluster analysis on wind data, and (iii) conditional probability function (CPF). The percentage of elements in PM2.5 ranged between 11 and 20%, and Ca and S were the most abundant elements in the region. Typical seasonal variations and similar trends were exhibited by each element, especially in the lowland. Some elements such as Zn, K, Mn, Pb, and Sb were found at high concentrations during the cold period. However, no similar dispersion processes were observed throughout the region, and their concentrations were mostly depending on individual local sources. In the alpine and foothill parts of the region, lower concentrations were recorded with respect to the Po Valley cities, which resulted enriched of most of the elements considered in this study. The cluster analysis on wind data and the CPF of the ratio-related sources demonstrated that a widespread pollution condition exists in the region, apart from the coastal area. However, specific directions (e.g., a link with high-traffic roads, industrial areas, and airports) resulted the most probable explanation for each ratio-related source. In addition, the Veneto region hosts one of the most important Mediterranean ports for the cruise sector (Venice harbor), and its impact was previously demonstrated in the historical city center. In this study, the impact of Venice shipping emissions was estimated to be 3.5% of PM2.5 in some particular days.

Influence of seasonality, air mass origin and particulate matter chemical composition on airborne bacterial community structure in the Po Valley, Italy.

The integration of chemical and biological data in aerosol studies represents a new challenge in atmospheric science. In this perspective it will be possible to gain a clearer and deeper comprehension of biogeochemical cycles in the atmosphere. In this view, this study aimed to investigate the relationships occurring between bacterial populations and PM chemical composition in one of the most polluted and urbanized areas in Europe: the Po Valley (Italy). Moreover, seasonality, long- and short-range transports were also evaluated to investigate the influence on airborne bacterial communities. PM samples were collected in two cities of the Po Valley (Milan and Venice) characterized by different meteorological conditions and atmospheric pollutant sources. Samples were analysed for water-soluble inorganic ions (WSIIs) and bacterial community structure. Chemical and biological data were jointly processed by using redundancy discriminate analysis (RDA), while the influence of atmospheric circulation was evaluated by using wind ground data and back-trajectories analysis. Results showed strong seasonal shifts of bacterial community structure in both cities, while a different behaviour was observed for air mass circulation at Milan ad Venice sites: long-range transport significantly affected bacterial populations in Milan whereas local ground wind had more influence in the Venice area. Moreover, difference in taxonomic composition can be mostly addressed to the characteristics of sampling sites. This evidence could suggest that, while PM composition is influenced by long-range transport, bacterial populations are affected, besides transport, by other factors (i.e., season and sampling site location). This perspective allow to better understand and explain airborne bacterial community behaviour.

Interannual heavy element and nutrient concentration trends in the top sediments of Venice Lagoon (Italy).

The elemental composition of surficial sediments of Venice Lagoon (Italy) in 1987, 1993, 1998 and 2003 were investigated. Zn and Cr concentrations resulted in higher than background levels, but only Cd and Hg were higher than legal quality standards (Italian Decree 2010/260 and Water Framework Directive 2000/60/EC). Contaminants with similar spatial distribution are sorted into three groups by means of correlation analysis: (i) As, Co, Cd, Cu, Fe, Pb, Zn; (ii) Ni, Cr; (iii) Hg. Interannual concentrations are compared by applying a factor analysis to the matrix of differences between subsequent samplings. A general decrease of heavy metal levels is observed from 1987 to 1993, whereas particularly high concentrations of Ni and Cr are recorded in 1998 as a consequence of intense clam fishing, subsequently mitigated by better prevention of illegal harvesting. Due to the major role played by anthropogenic sediment resuspension, bathymetric variations are also considered.

The PM2.5 chemical composition in an industrial zone included in a large urban settlement: main sources and local background.

Chemical analyses, receptor modeling and meteorological data were combined to determine the composition and sources of PM2.5 sampled daily in a large area in Italy characterized by a high number of heterogeneous industrial emissions and contiguous to a major urban center. The PM2.5 local background in the area, i.e. the common basic composition and concentrations of PM2.5, was determined. Factor analysis-multiple linear regression analysis (FA-MLRA) was used to identify and quantify the main PM sources. Groups of samples with similar source contributions were then sorted using cluster analysis. The potential source location and the influence of long range transport were investigated by using the conditional probability function (CPF) and the potential source contribution function (PSCF) respectively. On an annual basis, five sources of PM were found relevant. Industrial emissions accounted for 3% of PM mass, whereas the main contribution to PM was related to a combination of ammonium nitrate, combustion (54%) and road traffic (36%), mainly related to urban emissions. The PM2.5 background was estimated to account for 20 µg m(-3). It comprises contributions of 55% ammonium nitrate and combustion, 46% road traffic, 6% fossil fuel combustion and 3% industrial emissions. Source contributions are influenced by both local atmospheric circulation and regional transport.

Geochemical characterization of PM10 emitted by glass factories in Murano, Venice (Italy).

The atmosphere in Venice, like in other European cities, is influenced by complex PM(10) multi-emission sources with a net tendency to exceed the limits fixed by the directive 99/30/EC. This study investigated the composition of an ensemble of similar industrial sources, the Murano Glassmaking Factories (MGFs), and their influence on the Venice air quality, using a modelling approach, statistical analysis and geochemical considerations. Preliminary modelling simulations were conducted to select three sampling sites along the way of preferential transport of pollutants from source between February and April 2003. Subsequently, a sampling campaign was carried out in the same period of simulations. Concentrations of PM(10), eight major elements (Al, Ti, Ca, Mg, Na, K, Fe, Mn), 20 minor and trace elements (Li, V, Cr, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ru, Rh, Cd, Sb, Ba, Ce, Pt, Pb) and four PAHs (BaA, BbF, BkF, BaP) were quantified. The analytical results were statistically processed for exploring the relationships between inorganic elements and organic compounds, and results were interpreted using geochemical considerations. Results show a MGF component of PM(10) characterised by two different fingerprints: the first linked to glass raw material composition and the second mainly related to glass additives. Particularly, Cd, Se, As and Li preserve their ratios in all study area, and are interpreted as principal components of the MGF emissions. Other fingerprints can be traced to urban sources from the Venetian mainland.

Correlations among inorganic and organic elements in particulate matter (PM10) in urban area of Venezia-Mestre.

Concentrations of inhalable particulate matter (PM10), Pb, Zn, Pt, Ce, Cd, Se and of Benzo(a)pyrene (BaP) were determined in three locations near Venice from September 2000 to September 2001. Meteorological conditions were considered during the sampling period. All components showed higher concentrations during winter, except for Cd and Se in the two sites at Mestre. Spatial and temporal variations were observed. There were correlations between Pb and Zn and PM10, Cd and Se, Pb and BaP and, in the main street sampling site, also between BaP and Pt. Their possible sources of emission are discussed on the basis of correlations among elements.