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Airborne particulate matter (PM) is studied because of its effects on human health and climate change. PM long-term characterisation allows identifying trends and evaluating the outcomes of environmental protection policies. This work is aimed to study the inter-annual variability of PM2.5 and PM10 concentrations and chemical composition in an urban background site (Italy). A dataset of daily PM2.5 and PM10 was collected in the period 2016-2017, including the content of OC, EC, major water-soluble ions, main metals, and compared to a similar dataset collected in the period 2013-2014. Oxidative potential using DTT assay (dithiothreitol) was evaluated and expressed in DTTV as 0.39nmol/min·m3 in PM10 and 0.29 in PM2.5nmol/min·m3. PM source apportionment was computed using the EPA PMF5.0 model and source contributions compared with those of a previous dataset collected between 2013 and 2014. Multi linear regression analysis identified which source contributed (p&nbsp

The present study was developed on the following evidence: "what is considered to be environmentally sustainable in the technosphere has to be in compliance with the development tendency of the ecosphere". Starting from this hypothesis, two entropy-based indicators were proposed: the specific entropy per amount of exergy gained (SEEG); the specific entropy per amount of exergy exploitable in the technosphere (SEEE). These were retrieved from the specific entropy (SE) indicator largely exploited for assessing the health status and the development tendency of ecosystems. Entropy based indicators SEEG and SEEE were used for assessing the environmental sustainability of incineration, anaerobic digestion and composting of waste. The aim of these indicators was to support already available methodologies for environmental impact assessment for better understating the intrinsic sustainability of specific processes, since the only quantification of the emission appears not enough informative for this goal. Concerning the ecosphere, SE minimization follows the Darwinian principle "survival of the fittest", being the fittest ecosystems those able to make the most efficient and effective use and storage of energy and materials, at the lower relative entropy generation. Consequently, the lower are SEEG and SEEE the fittest is the analysed system (i.e. sustainable). Main findings indicate SEEG ranging from 2.471 to 3.705, for incinerator, from 0.007 to 0.106 for anaerobic digestion whereas resulted constant = 0.266 for composting. The SEEE ranged from 0.433 to 0.484 for incinerator, from0.001 to 0.008 for anaerobic digestion and resulted constant = 0.014 for composting. These preliminary results indicates that processes and system able to return chemicals and materials exploitable at technosphere level were characterized by higher ability in returning exergy flows at the lower entropy increase compared to hose returning only energy.

Populated coastal areas are exposed to emissions from harbour-related activities (ship traffic, loading/unloading, and internal vehicular traffic), posing public health issues and environmental pressures on climate. Due to the strategic geographical position of Italy and the high number of ports along coastlines, an increasing concern about maritime emissions from Italian harbours has been made explicit in the EU and IMO (International Maritime Organization, London, UK) agenda, also supporting the inclusion in a potential Mediterranean emission control area (MedECA). This work reviews the main available outcomes concerning shipping (and harbours’) contributions to local air quality, particularly in terms of concentration of particulate matter (PM) and gaseous pollutants (mainly nitrogen and sulphur oxides), in the main Italian hubs. Maritime emissions from literature and disaggregated emission inventories are discussed. Furthermore, estimated impacts to air quality, obtained with dispersion and receptor modeling approaches, which are the most commonly applied methodologies, are discussed. Results show a certain variability that suggests the necessity of harmonization among methods and input data in order to compare results. The analysis gives a picture of the effects of this pollution source, which could be useful for implementing effective mitigation strategies at a national level.

POST-PRINT VERSION The sources impacting size-segregated aerosol were studied in Venice (Italy), in the framework of the ECOMOBILITY project (ECOlogical supporting for traffic Management in cOastal areas By using an InteLlIgenT sYstem, Interreg Italy-Croatia). The importance of this work lies in the fact that aerosol can have a different impact on human health, based on the particle size: nanoparticles could be potentially more dangerous with respect to coarse and fine particles; at the same time, they are poorly studied. The aim of this work is to perform an overview of the chemical composition of size-segregated aerosol, for carrying out a size-dependent source apportionment of aerosol in the urban area of Venice. Aerosol was collected with a MOUDI 110 cascade impactor. After the gravimetric analysis, filters were divided in three parts and each piece underwent a different analytical procedure, for the analysis of trace metals, carbonaceous and ionic species. Source apportionment was conducted using two different approaches: i) approximate formulae; ii) Positive Matrix Factorization. Sea spray aerosol was found mainly in the coarse fraction. The fine fraction was dominated by secondary inorganic aerosol and organic aerosol. Primary anthropogenic aerosol increased as particle dimension decreased. For the first time, the contribution of shipping emission was investigated using chemical tracers on different size ranges below 1 µm and reaching nanoparticles (

Although biogas production can have some benefits, there is a research gap on potential influence of biogas plant emissions on local air quality, thus an accurate and comprehensive evaluation of impacts of this technology is needed. This study deals with this issue by means of a characterisation of air pollution near an industrial area including a biogas production (from biomass) and combustion plant located in South Italy. The methodology consists in advanced statistical analysis on concentration of gaseous pollutants, particles concentration and size distribution in number and mass, and PM2.5 chemical composition. High-temporal resolution measurements, supported by ancillary meteorological parameters, and source apportionment of PM2.5 using Positive Matrix Factorization (PMF) receptor model, are performed. The integrated approach provides the emissive picture consisting in different anthropogenic sources (i.e. traffic, biomass burning, and industrial facilities) with particular focus on biogas plant emissions. Results showed that CO and nitrogen oxides were influenced by vehicular traffic and biomass combustion, however, a contribution of the plant to NO was observed. SO2 was influenced mainly by transport from the industrial zone, but a second local contribution compatible with the emissions of the biogas plant was detected. Number particle concentrations were analysed in four size ranges: nanoparticles (D < 0.05 ?m), ultrafine particles (D < 0.3 ?m), accumulation (0.3 < D < 1 ?m) and coarse particles (D > 1 ?m). Nanoparticles and ultrafine particles were mainly influenced by vehicular traffic and biomass burning, instead, a contribution of the plant was individuated in the accumulation mode. PMF5 identified the contribution of six sources: crustal (14.7% ± 2.1% of measured PM2.5); marine aerosol (aged) (12.9% ± 2.3%); biomass burning (32.8% ± 1.4%); secondary sulphate (19.7% ± 2.4%); primary industrial emissions (5.4% ± 2.3%); traffic and secondary nitrate (17.0% ± 3.9%). The plant is likely to contribute to both sources, the industrial and the traffic plus secondary nitrate. © 2020 Elsevier B.V.

Saharan dust (SD) is a relevant source of mineral particles (PM) for the Mediterranean region with potential impacts on air quality and climate. In this work, a long-term analysis of 56 SD events recorded between 2013 and 2018 at the Environmental-Climate Observatory of Lecce (SE Italy) was performed to investigate the effects and the seasonality of dust advection on PM2.5 and PM10, on carbon content, and on number and mass size distributions. The average duration of events was 2.6 days (10% of days) with a pronounced seasonality, 12.5% during warm seasons and 7.5% during cold seasons. The average contribution to PM10 was 1.5 μg/m3, between 1.4 μg/m3 (cold seasons) and 1.8 μg/m3 (warm seasons). Contribution to PM2.5 was significantly lower and not negligible during warm seasons (0.5 μg/m3). The impact of SD in south-eastern Italy is comparable with that in central Italy rather than to that observed in south-western Italy. Looking at PM10, 70 days exceeding legislation threshold were observed (4.8% of days), 22.9% of these exceedances were during SD. Extreme SD events (contributions > 100 μg/m3) cover 2% of the cases. Comparison of carbon content between SD and non-SD days shows that SD does not influence EC and eBC concentrations; however, SD contributes to secondary organic aerosol in the coarse fraction (PM10-2.5). Size distributions (in number and mass) measured during SD and non-SD days show that SD increases the particle number concentrations for diameters (Dp) larger than about 0.9–1 μm. Maximum increase was for Dp 2.5–3 μm.

Size-segregated analysis of organic and elemental carbon (EC, OC) in aerosol is essential in understanding sources and effects on the environment. However, these studies are scarce, especially in coastal areas stressed by anthropogenic emissions and with interactions between anthropogenic and natural emissions. To partially fill this lack of information, aerosol size segregated samples were taken between August 2018 and May 2019, using a MOUDI impactor. Measurements were performed in two port-cities of Northern Adriatic Sea, Venice (Italy) and Rijeka (Croatia). A thermal-optical analysis (EUSAAR2) allowed EC and OC determination in different size ranges. For Rijeka site, the water soluble organic carbon content (WSOC) was analysed. OC and EC average concentrations in Venice were 3.16 (+/- 0.97) and 0.40 (+/- 0.13) mu g/m(3); in Rijeka: 2.48 (+/- 0.65) and 0.37 (+/- 0.08) mu g/m(3). The OC size distributions were bimodal at both sites, with an accumulation mode in the size range 0.56-0.32 mu m, a coarse mode in the range 5.6-3.2 mu m. EC showed a bimodal distribution in Rijeka, a single fine mode in Venice. The EC/TC ratio was large in the fine mode at both sites, however, in Rijeka non-negligible values were found in the coarse fraction suggesting contributions from resuspension of carbon-loaded dust and mixing of anthropogenic particles with sea spray. The WSOC/OC analysis as function of particle size in Rijeka showed a total value of 0.51 (+/- 0.12) with an increase in the coarse fraction likely due to contributions of water soluble carbon from sea spray and biogenic emissions.

Some studies suggested a role of the atmospheric particulate matter (PM) and of its oxidative potential (OP) in determining adverse health effects. Several works have focused on characterisation of source contributions to PM OP, mainly using three approaches: correlation between OP and chemical markers of specific sources, use of OP as input variable in source apportionment with receptor models, and multi-linear regression (MLR) between OP and source contributions to PM obtained from receptor models. Up to now, comparison of results obtained with different approaches on the same dataset is scarce. This work aims to perform a OP study of PM2.5 collected in an industrial site, located near a biogas production and combustion plant (in southern Italy), comparing different approaches to investigate the contributions of the different sources to OP. The PM2.5 samples were analysed for determining ions, metals, carbonaceous components, and OP activity with the DTT (dithiotreitol) assay. Results showed that OP normalised in volume (DTTV) is correlated with carbonaceous components and some ions (NO3&minus, and Ca2+) indicating that PM of combustion, secondary, and crustal origin could contribute to the OP activity. The source apportionment, done with the Environmental Protection Agency (EPA)&mdash, Positive Matrix Factorization (PMF5.0) model, identified six sources: secondary sulphate, biomass burning, industrial emissions, crustal, vehicle traffic and secondary nitrate, and sea spray. A MLR analysis between the source&rsquo, s daily contributions and the daily DTTV values showed a reasonable agreement of the two approaches (PMF and MLR), identifying the biomass burning and the vehicle traffic and secondary nitrate as the main sources contributing to DTTV activity.

Accurate measurements of total mercury (HgT) in wet precipitation samples, collected in the suburban area of Cosenza (Southern Italy), over a 2-year period, from November 2013 to February 2016, were performed to study the distribution of rainwater HgT concentra ons and to evaluate the seasonal contribution of wet deposi on to the Hg flux . Precipitation samples were collected using a wet-only collector at the sampling site (39°21'N, 16°13'E, 217 m a.s.l.) inside the Campus of UniCal (University of Calabria) in Rende, Italy, following harmonized sampling procedures reported in the Standard Operating Procedures (SOPs) of the GMOS project. The volume weighted mean (VWM) of total mercury concentrations in 2014 and 2015 were 7.1 ± 3.9 ng L-1 and 15.1 ± 10.4 ng L-1 (mean ± SD), respectively, whilst the wet deposition flux of HgT in 2014 and 2015 were 6.1 ?g m-2 y-1 and 17.1 ?g m-2 y-1, respectively. Seasonal VWM HgT concentrations in 2014 shows highest values in spring followed by winter, summer, and fall. In 2015, VWM HgT concentrations were characterized by highest Hg levels in summer followed by spring, fall, and winter. In 2014, the wet deposition fluxes of HgT were in the order of spring > winter>fall>summer, while for the 2015 the largest wet deposition flux was observed in fall, due to the more abundant rainfall events, followed by winter, summer, and spring, respectively. In order to understand the potential mercury sources in precipitation during the period of this study, atmospheric pollutants (PM10, PM2.5, O3, NOx, SO2), local meteorological parameters, back trajectories (NOAA Hysplit) and satellite observation tools for wildfire/biomass burning events have been considered and their contribution was singled out. This work concerns Hg in wet deposition and an assessment of the occurrence and possible sources of rainwater HgT. This has been done using information that was not previously available to estimate the impact of mercury due to wet deposition in Southern Italy.

LIST OF CONTENTS. 1.Sampling; 2. Particulate matter concentration; 2.1.Material and methods; 2.2.Results and discussion; 3.Analysis of ions; 3.1.Material and methods; 3.2.Results and discussion; Distribution of ions in particulate matter; Size distribution of ions; 4.Analysis of metals; 4.1.Material and methods; 4.2.Results and discussion; Distribution of metals in particulate matter; Size distribution of metals; 5.Analysis of carbon; 5.1.Material and methods; 5.2.Results and discussion; Distribution of carbon in particulate matter; Size distribution of carbon; 6.Analysis of polycyclic aromatic hydrocarbons; 6.1.Material and methods 6.2.Results and discussion; Distribution of PAHs in particulate matter; Size distribution of PAHs; 7.Measurement campaign; 7.1.Material and methods; 7.2.Results and discussion; Meteorology during the campaign; Particle number concentrations and size distributions.

Two papers will be coordinated by ISAC - CNR and they are in preparation. The first one will be based on high-temporal resolution measurements of particle concentration in number and mass (in different sizes ranging from 0.01 to 32 ?m) and relative meteorological parameters, taken in both experimental sites (Venice and Rijeka). Furthermore, since the same instrumental setup was used, a possible comparison with previous works performed in Adriatic harbours, like Brindisi and Venice, will be reported, estimating ship traffic contribution in each port-city. The second study could be focused on elemental and organic carbon (EC, OC) determinations carried out from size segregated particulate samples collected in both sites by a 10-stages micro-orifice impactor (MOUDI 110NR) equipped with quartz fiber filters. Results of both campaigns will be compared and discussed interpreting the differences observed in the two sites. This will be one of the few studies in speciation of carbonaceous aerosol in different size ranges, obtaining size distribution of EC and OC in a harbour area. In fact, the most scientific literature aims to characterize particulate (PM10 or PM2.5) without analyzing chemical components distribution in function to particle size. The last two publications have been coordinated by University Ca' Foscari of Venice and University of Rijeka. In one of these, a complete chemical analysis (major iones, trace metals, and carbonaceous species) of size-segregated samples collected in Venice was performed followed by the application of the PMF (Positive Matrix Factorization) receptor model to investigate the contributions of the different sources acting on the area putting in evidence the weight of shipping compared to the other sources. The second paper is based on a similar post-processing applied to the size-segregated samples collected in Rijeka.

This report tries to fill some of these gaps applying the methodologies based on both chemical characterization of particulate matter and high-temporal resolution online measurements, used in the POSEIDON project (Pollution Monitoring of ship emissions: an Integrated approach for harbours in the Adriatic basin, Interreg MED program 2007-2013) that is capitalized in ECOMOBILITY, to characterize the impact of ship traffic to particulate matter of different size starting from nanoparticles and up to PM10. The same approach and the same measurement instruments have been used in the two areas (Venice and Rijeka) to ensure comparability of results. The report is organized in the following sections: 1) Chapter 1 is the introduction; 2) Chapter 2 describes the methodology used for post-processing high-temporal resolution data; 3) Chapter 3 describes the methodology used for post-processing of size-segregated chemical composition; 4) Chapter 4 summarises data previously available in Venice and Rijeka regarding the impact of shipping to atmospheric particulate matter; 5) Chapter 5 discusses the results obtained in ECOMOBILITY regarding the impact of shipping to atmospheric particles of different size obtained; 6) Chapter 6 includes a comparison of the impacts of shipping to atmospheric particulate matter in Venice and Rijeka; 7) Conclusions and bibliographic references follow.

Exposure to atmospheric particulate matter (PM) leads to adverse health effects and the exact mechanisms of toxicity are still not completely understood. Recent studies suggested that a large number of PM health effects could be due to the oxidative potential (OP) of ambient particles leading to high concentrations of reactive oxygen species (ROS). However, information about the OP of natural sources are scarce and no data is available regarding the OP during Saharan dust outbreaks (SDO) in Mediterranean regions. This work uses the a-cellular DTT (dithiothreitol) assay to evaluate OP of the water-soluble fraction of PM2. 5 and PM10 collected at an urban background site in Southern Italy

Shipping is a growing transport sector representing a relevant share of atmospheric pollutant emissions at global scale. In the Mediterranean Sea, shipping affects air quality of coastal urban areas with potential hazardous effects on both human health and climate. The high number of different approaches for investigating this aspect limits the comparability of results. Furthermore, limited information regarding the inter-annual trends of shipping impacts is available. In this work, an approach integrating emission inventory, numerical modelling (WRF-CAMx modelling system), and experimental measurements at high and low temporal resolution is used to investigate air quality shipping impact in the Adriatic/Ionian area focusing on four port-cities: Brindisi and Venice (Italy), Patras (Greece), and Rijeka (Croatia). Results showed shipping emissions of particulate matter (PM) and NOx comparable to road traffic emissions at all port-cities, with larger contributions to local SO2 emissions. Contributions to PM2.5 ranged between 0.5% (Rijeka) and 7.4% (Brindisi), those to PM10 were between 0.3% (Rijeka) and 5.8% (Brindisi). Contributions to particle number concentration (PNC) showed an impact 2-4 times larger with respect to that on mass concentrations. Shipping impact on gaseous pollutants are larger than those to PM. The contribution to total polycyclic aromatic hydrocarbon (PAHs) concentrations was 82% in Venice and 56% in Brindisi, with a different partition gas-particle because of different meteorological conditions. The inter-annual trends analysis showed the primary contribution to PM concentrations decreasing, due to the implementation of the European legislation on the use of low-sulphur content fuels. This effect was not present on other pollutants like PAHs. (C) 2016 Elsevier Ltd. All rights reserved.

Shipping is one of the transport sectors less regulated, although more than 80% of world trade is transported by ships [1] and its share of total anthropogenic emissions is significant, with effects on climate, human health and air quality, especially in coastal areas. Recent studies [2] demonstrated the effectiveness of implementation of the 2005/33/EC European Directive in reducing the impact of ship traffic on aerosol concentrations at local scale, however, the effect on climate is more uncertain. Detailed information regarding the size distribution of the impacts to particles and their correlation with gaseous emissions is needed to investigate the complex air quality-climate interaction of this source. Much of the literature studies focus on NOX, SO2, and particulate matter (PM) emissions while there is a gap of knowledge about the size distribution of emitted particles, especially in coarse fraction. This study was done in the framework of POSEIDON (POllution monitoring of Ship Emission: an IntegrateD approach fOr harbour of the Adriatic basiN) project (MED 2007-2013). The aim was to estimate the contribution of in-port ship emissions to gaseous atmospheric pollutants and to PM of different sizes in a port-city in South-Eastern Italy (Adriatic Sea), after the enforcement of the low-sulphur fuel EU-Directive. Measurements were taken at high temporal resolution at the Passenger Terminal site in the harbour area of Brindisi (40° 38? 43.32? N-17° 57? 36.39? E). Data collected by a Mobile Laboratory, were gaseous pollutants (NO2, NO, O3, SO2; 5 min resolution), particle number concentrations (PNC; 1 min resolution), particle size distribution in the range 0.25-32 ?m (1 min resolution) and NO2 and SO2 flow-rate emissions with a DOAS (Differential Optical Absorption Spectroscopy) remote-sensing system, called GASCOD (Gas Absorption Spectrometer Correlating Optical Differences). The Port Authority provided data of ship traffic and a video camera was used to synchronize all measurements and visually estimate number of vehicles (cars, trucks) during loading/unloading of ships at berth. Characterization of ship plumes in aspect of particle size, gaseous concentrations, duration, ratio NO/NO2, was performed. The impact analysis [3] was applied separating manoeuvring (arrival/departure of ships) and hotelling (loading/unloading activities) phases. Results showed that the primary contribution to PM1 and PM2.5 was significantly lower with respect to those to PNC for both phases, confirming that the majority of the particles emitted were in the ultrafine size range. Manoeuvring phase was characterized by higher impacts to SO2, NO, and NO2 than those to PNC, PM1 and PM2.5. Hotelling phase represented a significant share of the impact for NO, NO2, PNC but gave a low contribution to SO2 impact (due to low-sulphur fuel). Ultrafine particles (Dp1) fraction while accumulation mode particles (0.25

Shipping is one of the transport sectors less regulated, although more than 80% of world trade is transported by ships [1] and its share of total anthropogenic emissions is significant, with effects on climate, human health and air quality, especially in coastal areas. Recent studies [2] demonstrated the effectiveness of implementation of the 2005/33/EC European Directive in reducing the impact of ship traffic on aerosol concentrations at local scale, however, the effect on climate is more uncertain. Detailed information regarding the size distribution of the impacts to particles and their correlation with gaseous emissions is needed to investigate the complex air quality-climate interaction of this source. Much of the literature studies focus on NO X , SO 2 , and particulate matter (PM) emissions while there is a gap of knowledge about the size distribution of emitted particles, especially in coarse fraction. This study was done in the framework of POSEIDON (POllution monitoring of Ship Emission: an IntegrateD approach fOr harbour of the Adriatic basiN) project (MED 2007-2013). The aim was to estimate the contribution of in-port ship emissions to gaseous atmospheric pollutants and to PM of different sizes in a port-city in South-Eastern Italy (Adriatic Sea), after the enforcement of the low-sulphur fuel EU-Directive. Measurements were taken at high temporal resolution at the Terminal Passeggeri site in the harbour area of Brindisi (40° 38? 43.32? N-17° 57? 36.39? E). Data collected by a Mobile Laboratory, were gaseous pollutants (NO 2 , NO, O 3 , SO 2 ; 5 min resolution), particle number concentrations (PNC; 1 min resolution), particle size distribution in the range 0.25-32 ?m (1 min resolution) and NO 2 and SO 2 flow-rate emissions with a DOAS (Differential Optical Absorption Spectroscopy) remote-sensing system. The Avvisatore Marittimo provided data of ship traffic in the harbour and a night & day video camera was used to synchronize all measurements and visually estimate number of vehicles (cars, trucks) passing on the framed docks, during phases of loading/unloading of ships at berth. Characterization of ship plumes in aspect of particle size, gaseous concentrations, duration, ratio NO/NO 2 , was performed. The impact analysis [3] was applied separating manoeuvring (arrival/departure of ships) and hotelling (loading/unloading activities) phases. Results showed that the primary contribution to PM 1 and PM 2.5 was significantly lower with respect to those to PNC for both phases, confirming that the majority of the particles emitted were in the ultrafine size range. Manoeuvring phase was characterized by higher impacts to SO 2 , NO, and NO 2 than those to PNC, PM 1 and PM 2.5 . Hotelling phase represented a significant share of the impact for NO, NO 2 , PNC but gave a low contribution to SO 2 impact (due to low-sulphur fuel). Ultrafine particles (D p 1) fraction while accumulation mode particles (0.25

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.

A measurement campaign was performed between 04/03/2013 and 17/07/2013 for simultaneous collection of PM 2.5 samples in two nearby sites in southeastern Italy: an urban site and an urban background site. PM 2.5 at the two sites were similar; however, the chemical composition and the contributions of the main sources were significantly different. The coefficients of divergence (CODs) showed spatial heterogeneity of EC (higher at the urban site because of traffic emissions) and of all metals. Major ions (NH 4 + , Na + , and SO 4 2 − ) and OC had low CODs, suggesting a homogeneous distribution of sea spray, secondary sulfate, and secondary organic matter (SOM = 1.6*OC sec , where OC sec is the secondary OC). The strong correlations between Na + and Cl − , and the low Cl − /Na + ratios, suggested the presence of aged sea spray with chloride depletion (about 79% of Cl − ) and formation of sodium nitrate at both sites. In both sites, the non-sea-salt sulfate was about 97% of sulfate, and the strong correlation between SO 4 2 − and NH 4 + indicated that ammonium was present as ammonium sulfate. However, during advection of Saharan Dust, calcium sulfate was present rather than ammonium sulfate. The source apportionment was performed using the Positive Matrix Factorization comparing outputs of model EPA PMF 3.0 and 5.0 version. Six aerosol sources were identified at both sites: traffic, biomass burning, crustal-resuspended dust, secondary nitrate, marine aerosol, and secondary sulfate. The PMF3.0 model was not completely able, in these sites, to separate marine contribution from secondary nitrate and secondary sulfate from OC, underestimating the marine contribution and overestimating the secondary sulfate with respect to stoichiometric calculations. The application of specific constraints on PMF5.0 provided cleaner profiles, improving the comparison with stoichiometric calculations. The seasonal trends revealed larger biomass burning contributions during the cold period at both sites due to domestic heating emissions added to those of agricultural practices. Secondary aerosol represented about 50% of PM 2.5 at both sites (about 1/3 due to SOM), with a slight increase during the cold season, probably due to the formation of secondary OC via gas-to-particle conversion. Secondary inorganic aerosol (nitrate plus sulfate) did not show seasonal trend because the reduction of nitrate due to thermal instability during the warm season was compensated by an almost equivalent increase of sulfate.

Harbours 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 abstract Impact 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.

Ship emissions are a growing concern, especially in coastal areas, for potential impacts on human health and climate. International mitigation strategies to curb these emission, based on low-sulphur content fuels, have proven useful to improve local air quality. However, the effect on climate forcing is less obvious. Detailed information on the influence of shipping to particles of different sizes is needed to investigate air quality and climate interaction. In this work, the contributions of maritime emissions to atmospheric concentrations of gaseous pollutants (NO, NO2, SO2, and O3) and of particles (sizes from 0.009 mm to 30 mm) were investigated considering manoeuvring (arrival and departure of ships) and hotelling phases (including loading/unloading activities). Results showed that the size distributions of shipping contributions were different for the two phases and could be efficiently described, using measured data, considering four size-ranges. The largest contribution to particles concentration was observed for Dp < 0.25 mm, however, a secondary maximum was observed at Dp ¼ 0.35 mm. The minimum contribution was observed at Dp around 0.8e0.9 mm with a negligible contribution from hotelling for size range 0.4e1 mm. The comparison of 2012 and 2014 datasets showed no significant changes of gaseous and particulate pollutant emissions and of the contribution to particle mass concentration. However, an increase of the contribution to particle number concentration (PNC) was observed. Results suggested that harbour logistic has a relevant role in determining the total impact of shipping on air quality of the nearby coastal areas. Additionally, future policies should focus on PNC that represents an important fraction of emissions also for low-sulphur fuels. DOAS remote sensing proved a useful tool to directly measure NO2 and SO2 ship emissions giving estimates comparable with those of emission inventory approach.

The performance and the uncertainty of receptor models (RMs) were assessed in intercomparison exercises employing real-world and synthetic input datasets. To that end, the results obtained by different practitioners using ten different RMs were compared with a reference. In order to explain the differences in the performances and uncertainties of the different approaches, the apportioned mass, the number of sources, the chemical profiles, the contribution-to-species and the time trends of the sources were all evaluated using the methodology described in Bells et al. (2015). In this study, 87% of the 344 source contribution estimates (SCEs) reported by participants in 47 different source apportionment model results met the 50% standard uncertainty quality objective established for the performance test. In addition, 68% of the SCE uncertainties reported in the results were coherent with the analytical uncertainties in the input data. The most used models, EPA-PMF v.3, PMF2 and EPA-CMB 8.2, presented quite satisfactory performances in the estimation of SCEs while unconstrained models, that do not account for the uncertainty in the input data (e.g. APCS and FA-MLRA), showed below average performance. Sources with well-defined chemical profiles and seasonal time trends, that make appreciable contributions (>10%), were those better quantified by the models while those with contributions to the PM mass close to 1% represented a challenge. The results of the assessment indicate that RMs are capable of estimating the contribution of the major pollution source categories over a given time window with a level of accuracy that is in line with the needs of air quality management. (C) 2015 The Authors. Published by Elsevier Ltd.

Ships and harbour emissions are currently increasing, due to the increase of tourism and trade, with potential impact on global air pollution and climate. At local scale, in-port ship emissions influence air quality in coastal areas impacting on health of coastal communities. International legislations to reduce ship emissions, both at Worldwide and European levels, are mainly based on the use of low-sulphur content fuel. In this work an analysis of the inter-annual trends of primary contribution, e, of tourist shipping to the atmospheric PM2.5 concentrations in the urban area of Venice has been performed. Measurements have been taken in the summer periods of 2007, 2009 and 2012. Results show a decrease of e from 7% (±1%) in 2007 to 5% (±1%) in 2009 and to 3.5% (±1%) in 2012. The meteorological and micrometeorological conditions of the campaigns were similar. Tourist ship traffic during measurement campaigns increased, in terms of gross tonnage, of about 25.4% from 2007 to 2009 and of 17.6% from 2009 to 2012. The decrease of e was associated to the effect of a voluntary agreement (Venice Blue Flag) for the use of low-sulphur content fuel enforced in the area between 2007 and 2009 and to the implementation of the 2005/33/CE Directive in 2010. Results show that the use of low-sulphur fuel could effectively reduce the impact of shipping to atmospheric primary particles at local scale. Further, voluntary agreement could also be effective in reducing the impact of shipping on local air quality in coastal areas.

Surface chemical composition of particles has a key role in determining the reactivity and optical properties of atmospheric aerosol. This composition depend on the particles sources and formation processes and it influences human health and climate. In this work, the X-ray photoelectron spectroscopy (XPS) has been used for the systematic surface characterization of atmospheric particles of different sizes, collected using a 10-stage MOUDI-II rotating cascade impactor in an urban background site. The high resolution XPS spectra allowed to distinguish different organic functional groups (C-C/CC, -C-O, -CO/-C(O)N, -C(O)O, C-O3=) and to speciate the detectable hetero-elements, sulphur (S-O42-, sulphone and sulphide compounds), nitrogen (N-H4+, N-O3-, N-O2- and organic-nitrogen compounds), sodium (Na+) and chlorine (Cl-) species. Significant differences in particles belonging to accumulation (small particles) and coarse (large particles) modes were observed being due to the formation processes and sources from which particles originated. The oxygen concentrations is inversely correlated with carbon concentrations, however, the content of oxidized organic carbon is not correlated with oxygen content confirming that the oxygen increment observed in large particles can likely be attributed to the contribution of inorganic species (crustal origin). The speciation of nitrogen showed ammonium only in the accumulation mode and nitrate only in coarse mode excluding the presence of ammonium nitrate of secondary origin in the area studied. A correlation of Na and Cl was attributed to the marine contribution with an excess of Cl on the surface correlated with the depletion of Cl observed in the bulk of particles. © 2015 Elsevier Ltd.

Samples of PM10 and PM2.5 were collected discontinuously between 2003 and 2010 at fifteen monitoring sites (urban, background, industrial) in the south-eastern part of Italy using a mobile laboratory. In total, 483 PM10 and 154 PM2.5 samples were collected and chemically analyzed for the determination of metal content. Data were used to investigate concentration differences among the typologies of sites, the seasonal patterns, and the influence of advection of Saharan dust (SD). PM10 and PM2.5 average concentrations increase from background to industrial and urban sites but the ratio PM2.5/PM10 is significantly lower (0.61 ± 0.10) in background sites. The average metals concentrations in PM10 and in PM2.5 do not show a clear dependence on site typology apart an increase in crustal elements in background sites and an increase in the enrichment factors of Ni and of Cr in PM10 in industrial sites. Urban sites show a statistically significant increase of PM10 average concentration during the cold seasons (autumn and winter), likely associated with the anthropogenic urban emissions, instead, the background sites show a decrease in concentrations during the cold seasons. This could be due to more frequent cases of SD observed in spring and summer periods that mainly influence background sites. The seasonal difference on the average concentration for industrial sites is not statistically significant. The SD cases influence both PM10 and PM2.5 concentrations but their effect is significantly larger on PM10. Over the studied area, the effect is relatively limited on long-term average PM10 (estimated increase of 3.2%) and PM2.5 (estimated increase of 1.5%) concentrations but it is significant on daily concentrations. It is estimated an increase of 22% of the probability to overcome the air quality standard daily threshold for PM10.

INTRODUCTION 2. SAMPLING AND ANALYSIS 2.1. Description of the area of interest 2.2. Sampling sites 2.3. Sampling and analysis of high temporal resolution PM2.5 and PNC 2.4. Sampling and analysis of PAHs 2.5. Sampling and analysis of metals in PM10 3. HIGH RESOLUTION PM2.5 AND PARTICLE NUMBER CONCENTRATIONS 3.1. Concentration of PM2.5 and particle number concentration 3.2. Direct contributions of ship traffic to PM2.5 and PNC 4. POLYCICLIC AROMATIC HYDROCARBONS (PAHs) 4.1. Concentration of PAHs over the years 4.2. Identification of potential sources of PAHs 4.3. Contribution of the harbour sector to PAHs 5. METALS IN PM10 5.1. Concentration of metals over the years 5.2. Evaluation of sources using PMF 6. CONCLUSIONS AND FUTURE PERSPECTIVES 7. ACKNOWLEDGEMENTS 8. BIBLIOGRAPHY

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.

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 PM 2.5 acting on the Brindisi harbour–industrial area, trying to pinpoint the contribution of in-port ship emissions to primary and secondary PM 2.5 . 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 PM 2.5 samples and characterising the concentrations of 23 chemical species (water soluble organic and inorganic carbon; major ions: SO 4 2 − , NO 3 − , NH 4 + , Cl − , C 2 O 4 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 PM 2.5 and were used for source apportionment via PMF. The contributions of eight sources were estimated: crustal (16.4 ± 0.9% of PM 2.5 ), 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 PM 2.5 (2.8% +/− 1.1%). The secondary contribution of oil combustion to non-sea-salt-sulphate, nssSO 4 2 − , was estimated to be 1.3 μg/m 3 (about 40% of total nssSO 4 2 − or 11% of PM 2.5 ).

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.

In this work, the inorganic chemical profiles of soil samples collected at different sites in the Salentum peninsula (Italy, Apulia region) are discussed. The samples were re-suspended in the laboratory, for PM10 sampling, using a ventilated wooden chamber and were then chemically analysed measuring the abundances of 17 elements. Different land use categories of soils (olive grove, arable land, vineyards, sand, and urban dust) were included in the 50 samples analysed: 45 collected in background areas and five collected in the urban area of Lecce. The objectives were to compare the chemical profiles of raw soil and re-suspended PM10 for different crustal sources and to estimate the potential improvements in the calculation of the enrichment factors of atmospheric PM10. The variability of elemental abundances in samples of the same category of soil collected in different zones was of the same order of magnitude as the differences observed between the various categories of soil. This allows the calculation of a weighted average composition of soil and urban dust and the corresponding weighted average composition of re-suspended PM10. In re-suspended PM10 from average background soil, all of the elements except Ca, Na, K and V have larger abundances with respect to raw soil. In urban dust, this is limited to Ca, V and Mg. The crustal enrichment factors (EFs) of atmospheric PM10 were evaluated by considering different reference elements and different reference tables. Results indicated that it is possible to apply a two-threshold (S-1 and S-2) scheme for the interpretation of EF, with thresholds derived from uncertainty in soil categories and from the choice of the reference element. A specific element is likely of crustal origin if EF < S-1 and likely of anthropogenic origin if EF > S-2. Between the two thresholds, the element can be considered of mixed origin. The thresholds vary according to the geological composition used in the evaluation of EF. If the average composition of local re-suspended soils is used, the thresholds are S-1 = 2 and S-2 = 4. If raw soil is used, the thresholds become S-1 = 5 and S-2 = 10. If the average upper-crust composition from literature data is used, the thresholds further increase to S-1 = 10 and S-2 = 20. (C) 2012 Elsevier Ltd. All rights reserved.

A structural and functional interaction between A(2A) adenosine receptors and D(2) dopamine receptors has been implicated in the pathophysiology of impulse control disorders. The aim of this study was to use platelet membranes to assess A(2A) adenosine receptor affinity and density in patients affected by pathological gambling (PG; which is classified as a specific impulse control disorder) with respect to those of control subjects.Twelve drug-free PG patients and 12 age- and sex-matched healthy controls were enrolled in the study. PG was diagnosed according to the Structured Clinical Interview for DSM-IV - Patient Version 2.0 and the South Oaks Gambling Screen. A(2A) adenosine receptor binding parameters were evaluated using a [(3)H]ZM(241385) binding assay; affinity and density (B(max)) were determined by means of saturation binding studies with platelet membranes.The A(2A) adenosine receptor binding affinity was found to be significantly higher in patients affected by PG than in healthy subjects; in contrast, no significant differences in B(max) were observed between the 2 groups.The elevated A(2A) adenosine receptor binding affinity in platelets from PG patients with respect to control subjects demonstrates for the first time a change in adenosine receptor parameters, and it suggests the involvement of the adenosine system in this pathology. The previously demonstrated hyperactivity of the dopamine system in PG may modulate the A(2A) adenosine receptor, supporting a role for this receptor as a peripheral marker of dopamine dysfunction. Because it is not possible to directly measure the D(2) dopamine receptor in human platelets, these data are particularly relevant to the detection of dopamine dysfunction.

Aerosol and gaseous pollution measurements were carried out at an urban background site in the south of Italy located near an industrial complex. Collection of 24 h samples of PM10 and PM2.5 and successive chemical quantification of metals were performed. Data were compared with measurements taken at a suburban background site, located at 25 km distance. The comparison showed the presence of an industrial contribution with a well defined chemical emission profile, similar, in terms of metals content, to urban emissions. As this made difficult the quantitative characterisation of the contribution of the two sources to atmospheric PM, a statistical method based on the treatment of data arising from high temporal resolution measurements was developed. Data were taken with a micrometeorological station based on an integrating nephelometer (Mie pDR-1200) for optical detection of PM2.5 concentration, with successive evaluation of vertical turbulent fluxes using the eddy-correlation method. Results show that the contribution from the two sources (urban emissions and industrial releases) have a very different behaviour, with the industrial contribution being present at high wind velocity with short concentration peaks (average duration 4 min) associated to strong positive and negative vertical fluxes. The estimated contribution to PM2.5 is 2.3% over long-term averages. The urban emissions are mainly present at low wind velocity, with longer concentration peaks in the morning and late evening hours, generally associated to small positive vertical fluxes. The characterisation of the contribution was performed using deposition velocity V(d) that is on average -3.5 mm s(-1) and has a diurnal pattern, with negligible values during the night and a minimum value of around -9 mm s(-1) late in the afternoon. Results show a correlation between V(d), friction velocity and wind velocity that could be the basis for a parameterisation of V(d) to be used in dispersion codes.

Global emissions reported by many authors have shown as natural and anthropic sources can contribute to the principal aerosol classes, but values change according the local scenario. The Venice Lagoon is exposed to different anthropic source emissions like vehicular traffic, industrial thermoelectric power plant, petrochemical plant, incinerator plant, domestic heating, ship traffic, glass factories and airport. Samplings of PM 2.5 were daily performed between March and November 2007 in Sacca San Biagio island (Venice), and values of PM 2.5 concentration and element concentration were obtained. Monthly average concentrations (μg m −3 ) during this period show higher values during the spring and the autumn. A good relationship between data obtained and concentration values from environmental local agencies is evidenced, both for PM 2.5 from urban area (Venezia Mestre), and for PM 10 sampled in the same area, as well as the influence of some meteorological parameters on PM 2.5 concentration sampled. Trace elements samples were measured by an Inductively Coupled Plasma-Quadrupole Mass Spectrometry (ICP-QMS), and values (ng m −3 and μg g −1 ) for elements regulated by European directives (As, Cd, Ni, Pb), as well as, other elements (Na, Al, K, Ti, V, Mn, Fe, Co, Zn, Se, Ag) are also reported. Data analysis by mean of Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF) pointed out four principal groups of elements like Mn–Fe–K, As–Se–Cd, V–Co, and Pb that could be assigned to specific sources of the Venetian wetland basin.