D. Cesari

Source apportionment of size-segregated atmospheric particles based on the major water-soluble components in Lecce (Italy).

Atmospheric aerosols have potential effects on human health, on the radiation balance, on climate, and on visibility. The understanding of these effects requires detailed knowledge of aerosol composition and size distributions and of how the different sources contribute to particles of different sizes. In this work, aerosol samples were collected using a 10-stage Micro-Orifice Uniform Deposit Impactor (MOUDI). Measurements were taken between February and October 2011 in an urban background site near Lecce (Apulia region, southeast of Italy). Samples were analysed to evaluate the concentrations of water-soluble ions (SO4(2-), NO3(-), NH4(+), Cl(-), Na(+), K(+), Mg(2+) and Ca(2+)) and of water-soluble organic and inorganic carbon. The aerosols were characterised by two modes, an accumulation mode having a mass median diameter (MMD) of 0.35 ± 0.02 μm, representing 51 ± 4% of the aerosols and a coarse mode (MMD=4.5 ± 0.4 μm), representing 49 ± 4% of the aerosols. The data were used to estimate the losses in the impactor by comparison with a low-volume sampler. The average loss in the MOUDI-collected aerosol was 19 ± 2%, and the largest loss was observed for NO3(-) (35 ± 10%). Significant losses were observed for Ca(2+) (16 ± 5%), SO4(2-) (19 ± 5%) and K(+) (10 ± 4%), whereas the losses for Na(+) and Mg(2+) were negligible. Size-segregated source apportionment was performed using Positive Matrix Factorization (PMF), which was applied separately to the coarse (size interval 1-18 μm) and accumulation (size interval 0.056-1 μm) modes. The PMF model was able to reasonably reconstruct the concentration in each size-range. The uncertainties in the source apportionment due to impactor losses were evaluated. In the accumulation mode, it was not possible to distinguish the traffic contribution from other combustion sources. In the coarse mode, it was not possible to efficiently separate nitrate from the contribution of crustal/resuspension origin.

Source apportionment of PM2.5 in the harbour-industrial area of Brindisi (Italy): identification and estimation of the contribution of in-port ship emissions.

Harbours are important for economic and social development of coastal areas but they also represent an anthropogenic source of emissions often located near urban centres and industrial areas. This increases the difficulties in distinguishing the harbour contribution with respect to other sources. The aim of this work is the characterisation of main sources of PM2.5 acting on the Brindisi harbour-industrial area, trying to pinpoint the contribution of in-port ship emissions to primary and secondary PM2.5. Brindisi is an important port-city of the Adriatic Sea considered a hot-spot for anthropogenic environmental pressures at National level. Measurements were performed collecting PM2.5 samples and characterising the concentrations of 23 chemical species (water soluble organic and inorganic carbon; major ions: SO4(2-), NO3(-), NH4(+), Cl(-), C2O4(2-), Na(+), K(+), Mg(2+), Ca(2+); and elements: Ni, Cu, V, Mn, As, Pb, Cr, Sb, Fe, Al, Zn, and Ti). These species represent, on average, 51.4% of PM2.5 and were used for source apportionment via PMF. The contributions of eight sources were estimated: crustal (16.4±0.9% of PM2.5), aged marine (2.6±0.5%), crustal carbonates (7.7±0.3%), ammonium sulphate (27.3±0.8%), biomass burning-fires (11.7±0.7%), traffic (16.4±1.7 %), industrial (0.4±0.3%) and a mixed source oil combustion-industrial including ship emissions in harbour (15.3±1.3%). The PMF did not separate the in-port ship emission contribution from industrial releases. The correlation of estimated contribution with meteorology showed directionality with an increase of oil combustion and sulphate contribution in the harbour direction with respect to the direction of the urban area and an increase of the V/Ni ratio. This allowed for the use of V as marker of primary ship contribution to PM2.5 (2.8%+/-1.1%). The secondary contribution of oil combustion to non-sea-salt-sulphate, nssSO4(2-), was estimated to be 1.3 μg/m(3) (about 40% of total nssSO4(2-) or 11% of PM2.5).

Comparison of PM10 concentrations and metal content in three different sites of the Venice Lagoon： An analysis of possible aerosol sources

The Venice Lagoon is exposed to atmospheric pollutants from industrial activities, thermoelectric power plants, petrochemical plants, incinerator, domestic heating, ship traffic, glass factories and vehicular emissions on the mainland. In 2005, construction began on the mobile dams (MOSE), one dam for each channel connecting the lagoon to the Adriatic Sea as a barrier against high tide. These construction works could represent an additional source of pollutants. PM10 samples were taken on random days between 2007 and 2010 at three different sites: Punta Sabbioni, Chioggia and Malamocco, located near the respective dam construction worksites. Chemical analyses of V, Cr, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl and Pb in PM10 samples were performed by Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) and results were used to identify the main aerosol sources. The correlation of measured data with meteorology, and source apportionment, failed to highlight a contribution specifically associated to the emissions of the MOSE construction works. The comparison of the measurements at the three sites showed a substantial homogeneity of metal concentrations in the area. Source apportionment with principal component analysis (PCA) and positive matrix factorization (PMF) showed that a four principal factors model could describe the sources of metals in PM10. Three of them were assigned to specific sources in the area and one was characterised as a source of mixed origin (anthropogenic and crustal). A specific anthropogenic source of PM10 rich in Ni and Cr, active at the Chioggia site, was also identified.

An inter-comparison of PM10 source apportionment using PCA and PMF receptor models in three European sites.

Source apportionment of aerosol is an important approach to investigate aerosol formation and transformation processes as well as to assess appropriate mitigation strategies and to investigate causes of non-compliance with air quality standards (Directive 2008/50/CE). Receptor models (RMs) based on chemical composition of aerosol measured at specific sites are a useful, and widely used, tool to perform source apportionment. However, an analysis of available studies in the scientific literature reveals heterogeneities in the approaches used, in terms of “working variables” such as the number of samples in the dataset and the number of chemical species used as well as in the modeling tools used. In this work, an inter-comparison of PM10 source apportionment results obtained at three European measurement sites is presented, using two receptor models: principal component analysis coupled with multi-linear regression analysis (PCA-MLRA) and positive matrix factorization (PMF). The inter-comparison focuses on source identification, quantification of source contribution to PM10, robustness of the results, and how these are influenced by the number of chemical species available in the datasets. Results show very similar component/factor profiles identified by PCA and PMF, with some discrepancies in the number of factors. The PMF model appears to be more suitable to separate secondary sulfate and secondary nitrate with respect to PCA at least in the datasets analyzed. Further, some difficulties have been observed with PCA in separating industrial and heavy oil combustion contributions. Commonly at all sites, the crustal contributions found with PCA were larger than those found with PMF, and the secondary inorganic aerosol contributions found by PCA were lower than those found by PMF. Site-dependent differences were also observed for traffic and marine contributions. The inter-comparison of source apportionment performed on complete datasets (using the full range of available chemical species) and incomplete datasets (with reduced number of chemical species) allowed to investigate the sensitivity of source apportionment (SA) results to the working variables used in the RMs. Results show that, at both sites, the profiles and the contributions of the different sources calculated with PMF are comparable within the estimated uncertainties indicating a good stability and robustness of PMF results. In contrast, PCA outputs are more sensitive to the chemical species present in the datasets. In PCA, the crustal contributions are higher in the incomplete datasets and the traffic contributions are significantly lower for incomplete datasets.

Application of PMF and CMB receptor models for the evaluation of the contribution of a large coal-fired power plant to PM10 concentrations

The evaluation of the contribution of coal-fired thermo-electrical power plants to particulate matter (PM) is important for environmental management, for evaluation of health risks, and for its potential influence on climate. The application of receptor models, based on chemical composition of PM, is not straightforward because the chemical profile of this source is loaded with Si and Al and it is collinear with the profile of crustal particles. In this work, a new methodology, based on Positive Matrix Factorization (PMF) receptor model and Si/Al diagnostic ratio, specifically developed to discriminate the coal-fired power plant contribution from the crustal contribution is discussed. The methodology was applied to daily PM10 samples collected in central Italy in proximity of a large coal-fired power plant. Samples were simultaneously collected at three sites between 2.8 and 5.8km from the power plant: an urban site, an urban background site, and a rural site. Chemical characterization included OC/EC concentrations, by thermo-optical method, ions concentrations (NH4(+), Ca(2+), Mg(2+), Na(+), K(+), Mg(2+), SO4(2-), NO3(-), Cl(-)), by high performances ion chromatography, and metals concentrations (Si, Al, Ti, V, Mn, Fe, Ni, Cu, Zn, Br), by Energy dispersive X-ray Fluorescence (ED-XRF). Results showed an average primary contribution of the power plant of 2% (±1%) in the area studied, with limited differences between the sites. Robustness of the methodology was tested inter-comparing the results with two independent evaluations: the first obtained using the Chemical Mass Balance (CMB) receptor model and the second correlating the Si-Al factor/source contribution of PMF with wind directions and Calpuff/Calmet dispersion model results. The contribution of the power plant to secondary ammonium sulphate was investigated using an approach that integrates dispersion model results and the receptor models (PMF and CMB), a sulphate contribution of 1.5% of PM10 (±0.3%) as average of the three sites was observed.

Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter in Venice air.

AbstractHarbours are important hubs for economic growth in both tourism and commercial activities. They are also an environmental burden being a source of atmospheric pollution often localized near cities and industrial complexes. The aim of this study is to quantify the relative contribution of maritime traffic and harbour activities to atmospheric pollutant concentration in the Venice lagoon. The impact of ship traffic was quantified on various pollutants that are not directly included in the current European legislation for shipping emission reduction: (i) gaseous and particulate PAHs; (ii) metals in PM10; and (iii) PM10 and PM2.5. All contributions were correlated with the tonnage of ships during the sampling periods and results were used to evaluate the impact of the European Directive 2005/33/EC on air quality in Venice comparing measurements taken before and after the application of the Directive (year 2010). The outcomes suggest that legislation on ship traffic, which focused on the issue of the emissions of sulphur oxides, could be an efficient method also to reduce the impact of shipping on primary particulate matter concentration; on the other hand, we did not observe a significant reduction in the contribution of ship traffic and harbour activities to particulate PAHs and metals. Graphical abstractImpact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter and evaluation of the effect of an European Directive on air quality in Venice

Electrochemical and Spectroscopic Behavior of Iron(III) Porphyrazines in Langmuir−Schäfer Films

Thin films of a newly synthesized iron(III) porphyrazine, LFeOESPz ( L = ClEtO, OESPz = ethylsulfanylporphyrazine), have been deposited by the Langmuir-Schafer (LS) technique (horizontal lifting) on ITO or gold substrates. Before deposition, the floating films have been investigated at the air-water interface by pressure/area per molecule (pi/ A) experiments, Brewster angle microscopy (BAM) and UV-vis reflection spectroscopy (RefSpec). The complex reacts with water subphase (pH 6.2) forming the mu-oxo dimer, which becomes the predominant component of the LS films ( LS-Fe) as indicated by optical, IR, XPS, and electrochemical data. LS-Fe multilayers exhibit, between open circuit potential (OCP) and +0.90 V (vs SCE), two independent peak pairs with formal potentials, E surf (I) and E surf(II) of +0.56 V and +0.78 V, respectively. According to dynamic voltammetric and coulometric experiments the peak pair at +0.56 V is attributed to one-electron process at the iron(III) centers on the monomer, while the peak pair at +0.78 V is associated to a four-electron process involving mu-oxo-dimer oligomers. LS-Fe films prove to be quite stable electrochemically between OCP and +0.90 V. The electrochemical stability decreases, however, when the potential range is extended both anodically and cathodically outside these limits, due to formation of new species. Upon incubation with TCA solutions, LS-Fe films show remarkable changes in the UV-vis spectra, which are consistent with a significant mu-oxo dimer --> monomer conversion. Addition of TCA to the electrochemical cell using a LS-Fe film as working electrode, results in a linear increase of a cathodic current peak near -0.40 V as the TCA concentration varies in the 0.1-2.0 mM range. This behavior is interpreted in terms of TCA inducing a progressive change in the composition of the LS-Fe films in favor of the monomeric iron(III) porphyrazine, which is responsible for the observed increase in the cathodic current near -0.40 V.

Characterisation of PM2,5 concentrations and turbulent fluxes on a island of the Venice Lagoon using high temporal resolution measurements

This work presents an analysis of PM2.5 concentrations and vertical turbulent fluxes on an island of the Venice lagoon. Data were collected during three measurement campaigns in spring, summer and winter periods. Measurements were taken with a high-resolution optical PM2.5 detector, coupled with a micrometeorological station that allowed the evaluation of the vertical turbulent fluxes of PM2.5 using the eddy-correlation technique. The main objective of this paper is to analyse the daily and seasonal pattern in PM2.5 concentrations and fluxes and to discuss their correlation with the main meteorological and micrometeorological parameters using high temporal resolution measurements. Observed data showed a seasonal pattern in turbulent fluxes with daytime average positive value during winter and negative during summer. Deposition velocities, ranged from –60 to 20 mm/s, appeared to be mainly influenced by atmospheric stability. There were larger emissions in cases of high wind velocities blowing from water sector indicating a significant potential contribution of sea spray to PM2.5 fluxes. The local atmospheric circulation, due to the orography of the area, was characterised by diurnal winds coming from the Adriatic Sea and nocturnal wind coming from the Alps. This circulation influenced deposition velocity creating an increase of negative fluxes in the morning at the starting of the sea breeze. A diurnal pattern in concentration has been observed and it is similar for all three measurement campaigns, with higher concentrations in nocturnal periods. The daily pattern was investigated in terms of its correlation with meteorological and micro-meteorological parameters, and was found highly correlated with the diurnal pattern of boundary layer height (BLH) and with relative humidity.

A Case Study of Municipal Solid Waste Landfills Impact on Air Pollution in South Areas of Italy

The average PM10 concentrations observed at Burgesi and Nardò landfills were comparable with the average of the territory while PM10 at Cavallino landfill was higher than the typical average. The VOC concentrations showed the predominant occurrence of the limonene and alfa-pynene compounds at all sites. Maximum concentrations of limonene and alfa-pynene were observed at Cavallino landfill. The PCDD/F and PCB concentrations showed significant variabilities among the different sites. It was noted that the average concentrations of the PCDD/F were higher at Nardò landfill. No particular correlations were observed between PCDD/F and PAH concentrations and between PCB and PAH concentrations.