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Atmospheric particulate matter (PM) is one of the major risks for global health. The exact mechanisms of toxicity are still not completely understood leading to contrasting results when different toxicity metrics are compared. In this work, PM10 was collected at three sites for the determination of acellular oxidative potential (OP), intracellular oxidative stress (OSGC), cytotoxicity (MTT assay), and genotoxicity (Comet assay). The in vitro tests were done on the A549 cell line. The objective was to investigate the correlations among acellular and intracellular toxicity indicators, the variability among the sites, and how these correlations were influenced by the main sources by using PMF receptor model coupled with MLR. The OPDTTV, OSGCV, and cytotoxicity were strongly influenced by combustion sources. Advection of African dust led to lower-than-average intrinsic toxicity indicators. OPDTTV and OSGCV showed site-dependent correlations suggesting that acellular OP may not be fully representative of the intracellular oxidative stress at all sites and conditions. Cytotoxicity correlated with both OPDTTV and OSGCV at two sites out of three and the strength of the correlation was larger with OSGCV. Genotoxicity was correlated with cytotoxicity at all sites and correlated with both, OPDTTV and OSGCV, at two sites out of three. Results suggest that several toxicity indicators are useful to gain a global picture of the potential health effects of PM.

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 PM

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.

Scientific interest is focusing on different approaches for characterising organic carbon (OC), elemental carbon (EC) and equivalent black carbon (eBC), although EUSAAR2 protocol has been established and frequently used in EU for regulatory purposes. Discrepancies are observed due to thermal protocols used for OC/EC determinations and the effect of the chemical-physical properties of aerosol using optical measurements for eBC. In this work, a long-term inter-comparison of carbon measurements with two widely used protocols (EUSAAR2 and NIOSH870) was performed on PM2.5 and PM10 samples. The influence of the protocol on the evaluation of secondary organic aerosol (SOC) and on the correlation between EC and eBC was investigated. An extensive check of repeatability gave typical uncertainties of ~ 5% for TC and OC, and ~ 10% for EC for both thermal protocols. Results show that OC is statistically comparable between the two protocols but EC is significantly higher with EUSAAR2, especially during the warm season. The ratio OC/EC is lower with EUSAAR2, also showing a seasonality (lower values in the warm season) not observed with NIOSH870. Despite the differences in OC/EC ratios, the contribution of SOC to OC (~ 50%), evaluated using the EC-tracer method, did not differ significantly between the two protocols and for both size fractions. Further, SOC/OC ratios were comparable in cold and warm periods. eBC/EC ratios larger than one for both protocols were obtained, 1.62 (EUSAAR2) and 1.92 (NIOSH870), and also correlated with the ratio OC/EC for both protocols, especially in the cold season.

Background In Italy the Law 9/2012 prescribed the total closure of forensic psychiatric hospitals (OPGs) and the conversion to a care model based on residential units in the community employing only clinical personnel (Residenze per l'Esecuzione delle Misure di Sicurezza – REMS) and fully integrated in public mental health services. The aim of this study is to report sociodemographic, clinical and criminological characteristics of patients admitted in Volterra REMS since it opened on 01/12/15 up to 31/12/17. Methods Sociodemographic and clinical information was collected from official documents (clinical files, ward reports) and from patients' personal health records. Psychiatric diagnoses were made by REMS psychiatrists according to the DSM-5 criteria. Criminological information was obtained from patients' criminal records. Results Volterra REMS patients' characteristics are similar to those of samples of OPGs patients (unmarried socially disadvantaged males with an average age of 40, no offsprings, low education, high rates of Schizophrenia Spectrum Disorders and medical comorbidity). However, the REMS model presents a very high turnover rate: during the study period 61 patients were admitted while 32 were discharged. Being assisted by public mental health services before committing the crime increased the probability of discharge. In non-EU patients long acting injectable antipsychotics were used more frequently than in community ones. Substance-Related Disorders are the main psychiatric comorbidity and resulted as being more frequent in bipolar patients than in other patients. Conclusions Due to the high patients' turnover, we expect a progressive change in sociodemographic, clinical and criminological features of the REMS population. The REMS model provides a return for mentally disordered criminals to the care of local public mental health services which are recovering after many years some of their most challenging patients ensuring their deinstitutionalization and reintegration into society.

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 (

Different powertrains passenger cars, homologate in compliance with Euro 6 standard, were compared in a life cycle perspective for assessing both environmental and human health impacts. For this latter aspect, some correlation between the emission of heavy metals, elemental carbon, organic carbon, the oxidative potential of particulate matter and the adverse effect on human health were also analyzed and discussed. Battery electric vehicle (BEV) showed the lower greenhouse gases emissions, from 0.1 kgCO2eq/km to 0.2 kgCO2eq/km but were charged by the higher emissions of freshwater eutrophication and freshwater ecotoxicity, about 6 × 10-6 kgPeq/km and 4 CTUe/km, respectively. Lower resource depletion was detected for cars powered by internal combustion and hybrid powertrains. Amount of particulate matter (PM) emitted resulted lower for petrol-hybrid electric vehicles (Petrol-HEV), of about 5 × 10-5 kgPM2.5eq/km. BEV were charged by the higher values of human toxicity cancer, from about 2 × 10-5 CTUh/km to about 5 × 10-5 CTUh/km whereas Petrol-HEV were credited by the lower impact on human health (DALY/km). The large contribution to PM emission from all the analyzed cars was from tyre and brake wear. Main PM components were elemental (ElC) and organic carbon (OC) compounds. ElC is also a specific marker of PM emitted from traffic. Both ElC and OC were characterized by a strong correlation with the oxidative potential of PM, indicating a threat for human respiratory tract only marginally decreased by the transition from conventional to electric poweretrains vehicles.

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.

This work presents and discusses the results of multi-year measurements of air toxicsconcentrations from different sites of Venice Lagoon. The aim of the study is thecharacterization of the air quality of the area, in terms of PM10, PM10-boundmetals,andpolycyclic aromatic hydrocarbons (PAHs) concentrations, even with the individuation ofthe related inhalation risk and the identification of the main contaminants’ sources. Thestudy moreover provides an important multi-years trend of chemical characterization ofthe Venice Lagoon. Sampling for PM10 and its metal content was carried out between2010 and 2015, using low volume sequential aerosol samplers; V, Cr, Fe, Co, Ni,Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb were measured by ICP-MS. Samples for PAHsconcentration in gas and particle phases were collected from 2010 to 2014, using ahigh-volume air sampler that allows to sample both phases simultaneously. Samplesfor PAHs determinations were analyzed by GC-HRMS. Concentrations of air toxicshave been studied with the use of enrichment factor, the coefficient of divergence, andthe Mann-Kendal test, to individuate eventual local divergences, seasonal and othertemporal trends. The inhalation risk assessment has been achieved by the calculation ofthe cumulative incremental carcinogenic risk for all the air toxics analyzed. The sources’identification and impact evaluation have been carried out using the atmosphericvanadium concentration, to calculate the primary contribution of ship traffic to PM10, thePositive Matrix Factorization, and the Diagnostic Ratios, with the aim of evaluating theimpact of construction activities of M.o.S.E, (Modulo Sperimentale Elettromeccanico-Electromechanical Experimental Module) as well as of ship traffic and other possible airtoxics’ sources. Temporal trends indicate a slight decrease of PAHs and PM10 and ofits content of Pb, Zn, Sb. Sharp increases of As and Cd during 2014 and 2015 maybe due to local sources like emissions from the construction yard, ship, and road traffic.The cumulative incremental carcinogenic risk was below the unconditionally acceptablerisk; Co and As are the most important contributors among metals, followed by Cdand Ni while the PAH congeners that most contribute to the carcinogenic risk werebenzo(a)pyrene and dibenzo(A,H)anthracene.

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.

Organic (OC) and Elemental Carbon (EC) are important components of atmospheric aerosol particles, playing a key role in climate system and potentially affecting human health. There is a lack of data reported for Southern Italy and this work aims to fill this gap, focusing the attention on the long-term trends of OC and EC concentrations in PM 2.5 and PM 10 , and on atmospheric processes and sources influencing seasonal variability. Measurements were taken at the Environmental-Climate Observatory of Lecce (SE Italy, 40°20′8″N-18°07′28″E, 37 m a.s.l.), regional station of the Global Atmosphere Watch program (GAW-WMO). Daily PM 10 and PM 2.5 samples were collected between July 2013 and July 2016. In addition, starting in December 2014, simultaneous equivalent Black Carbon (eBC) concentrations in PM 10 were measured using a Multi Angle Absorption Photometer. A subset of 722 PM samples (361 for each size fraction) was analysed by using a thermo-optical method with a Sunset Laboratory OC/EC analyser, to determine elemental and organic carbon concentrations. The average PM 10 and PM 2.5 concentrations were 28.8 μg/m 3 and 17.5 μg/m 3 . The average OC and EC concentrations in PM 10 were 5.4 μg/m 3 and 0.8 μg/m 3 , in PM 2.5 these were 4.7 μg/m 3 and 0.6 μg/m 3 . Carbonaceous content was larger during cold season with respect to warm season as well as secondary organic carbon (SOC) that was evaluated using the OC/EC minimum ratio method. SOC was mainly segregated in PM 2.5 and represented 53% - 75% of the total OC. A subset of EC data was compared with eBC measurements, showing a good correlation (R 2 = 0.80), however, eBC concentrations were higher than EC concentrations of an average factor of 1.95 (+/− 0.55 standard deviation). This could be explained by the presence of a contribution of Brown Carbon (BrC), for example from biomass burning, in eBC measurements. Weekly patterns showed a slight decrease of carbon content during weekends with respect to weekdays especially visible on eBC concentration due to the decrease of road traffic emissions. The daily patterns of hourly eBC concentrations showed a decrease in central diurnal hours, due to the cycle of planetary boundary-layer height, and concentrations peaks during rush hours due to road traffic emissions.

Comparison of fine and coarse fractions in terms of sources and dynamics is scarce in southeast Mediterranean countries; differences are relevant because of the importance of natural sources like sea spray and Saharan dust advection, because most of the monitoring networks are limited to PM10. In this work, the main seasonal variabilities of sources and processes involving fine and coarse PM (particulate matter) were studied at the Environmental-Climate Observatory of Lecce (Southern Italy). Simultaneous PM2.5 and PM10 samples were collected between July 2013 and July 2014 and chemically analysed to determine concentrations of several species: OC (organic carbon) and EC (elemental carbon) via thermo-optical analysis, 9 major ions via IC, and 23 metals via ICP-MS. Data was processed through mass closure analysis and Positive Matrix Factorization (PMF) receptor model characterizing seasonal variabilities of nine sources contributions. Organic and inorganic secondary aerosol accounts for 43% of PM2.5 and 12% of PM2.5–10 with small seasonal changes. SIA (secondary inorganic aerosol) seasonal pattern is opposite to that of SOC (secondary organic carbon). SOC is larger during the cold period, sulphate (the major contributor to SIA) is larger during summer. Two forms of nitrate were identified: NaNO3, correlated with chloride depletion and aging of sea-spray, mainly present in PM2.5–10; NH4NO3 more abundant in PM2.5. Biomass burning is a relevant source with larger contribution during autumn and winter because of the influence of domestic heating, however, is not negligible in spring and summer, because of the contributions of fires and agricultural practices. Mass closure analysis and PMF results identify two soil sources: crustal associated to long range transport and carbonates associated to local resuspended dust. Both sources contributes to the coarse fraction and have different dynamics with crustal source contributing mainly in high winds from SE conditions and carbonates during high winds from North direction.

This study was designed to assess the occurrence, relationships, sources, spatiotemporal variations, and source-specific multi-pathway cancer risk of PM2.5-bound PAHs at three urban environments in Tehran, Iran during a one-year campaign (2018–2019). The mean concentrations of PM2.5-bound ∑16PAHs were 24.6, 26.7, and 38.9 ng m−3 in HFT, AZD, and SHR sites, respectively. High molecular weight (HMW) PAHs were the main PAHs in the fine particle phase (76–83.4%) compare to low molecular weight (LMW) PAHs (16.6–24%). Redundancy analysis (RDA) showed that relative humidity (RH) and temperature (T) along with O3, NO2, and PM2.5 were critical driving factors affecting PAHs concentrations. Positive matrix factorization (PMF) extracted five PAHs emission sources: heavy-duty vehicles, light-duty vehicles, petrogenic, natural gas and coal/biomass combustion, industrial emissions, with different source contributions for each sampling site. The principal component analysis-multilinear regressions (PCA-MLR) and diagnostic ratios (DRs) methods indicated that the pyrogenic sources were the major sources of PM2.5-bound PAHs. The coefficient of divergence (COD) and Pearson correlation coefficient (R) of PAHs compounds and PMF derived source contributions (ng m−3) at paired sites indicated a relatively divergent spatiotemporal distribution. Based on incremental lifetime cancer risk (ILCR) levels of ∑PAHs source contributions, adults showed a more significant risk (1.33E-2.28E-05) than children (5.40E-9.22E-06). Source-specific-ILCR indicated that heavy-duty vehicles and natural gas-coal/biomass combustion emissions had the highest cancer risk contributions than the other apportioned sources.

Exposure to atmospheric particulate matter (PM) leads to adverse health effects although the exact mechanisms of toxicity are still poorly understood. Several 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). The contribution to OP of specific anthropogenic sources like road traffic, biomass burning, and industrial emissions has been investigated in several sites. 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. OP values in three groups of samples were compared: standard characterised by concentrations similar to the yearly averages; high carbon samples associated to combustion sources (mainly road traffic and biomass burning) and SDO events. DTT activity normalised by sampled air volume (DTTv), representative of personal exposure, and normalised by collected aerosol mass (DTTM), representing source-specific characteristics, were investigated. The DTTv is larger for high PM concentrations. DTTv is well correlated with secondary organic carbon concentration. An increased DTTv response was found for PM2.5 compared to the coarse fraction PM2.5-10. DTTv is larger for high carbon content samples but during SDO events is statistically comparable with that of standard samples. DTTM is larger for PM2,5 compared to PM10 and the relative difference between the two size fractions is maximised during SDO events. This indicates that Saharan dust advection is a natural source of particles having a lower specific OP with respect to the other sources acting on the area (for water-soluble fraction). OP should be taken into account in epidemiological studies to evaluate the potential health risks associated to ROS in regions affected by high pollution events due to Saharan dust advection. (C) 2017 Elsevier Ltd. All rights reserved.

Receptor models (RMs), based on chemical composition of particulate matter (PM), such as Chemical Mass Balance (CMB) and Positive Matrix Factorization (PMF), represent useful tools for determining the impact of PM sources to air quality. This information is useful, especially in areas influenced by anthropogenic activities, to plan mitigation strategies for environmental management. Recent inter-comparison of source apportionment (SA) results showed that one of the difficulties in the comparison of estimated source contributions is the compatibility of the sources, i.e. the chemical profiles of factor/sources used in receptor models. This suggests that SA based on integration of several RMs could give more stable and reliable solutions with respect to a single model. The aim of this work was to perform inter-comparison of PMF (using PMF3.0 and PMF5.0 codes) and CMB outputs, focusing on both source chemical profiles and estimates of source contributions. The dataset included 347 daily PM 10 samples collected in three sites in central Italy located near industrial emissions. Samples were chemically analysed for the concentrations of 21 chemical species (NH 4 + , Ca 2 + , Mg 2 + , Na + , K + , Mg 2 + , SO 4 2 − , NO 3 − , Cl − , Si, Al, Ti, V, Mn, Fe, Ni, Cu, Zn, Br, EC, and OC) used as input of RMs. The approach identified 9 factor/sources: marine, traffic, resuspended dust, biomass burning, secondary sulphate, secondary nitrate, crustal, coal combustion power plant and harbour-industrial. Results showed that the application of constraints in PMF5.0 improved interpretability of profiles and comparability of estimated source contributions with stoichiometric calculations. The inter-comparison of PMF and CMB gave significant differences for secondary nitrate, biomass burning, and harbour-industrial sources, due to non-compatibility of these source profiles that have local specificities. When these site-dependent specificities were taken into account, optimising the input source profiles of CMB, a significant improvement in the comparison of the estimated source contributions with PMF was obtained.

Scientific interest is focusing on different approaches for characterising organic carbon (OC), elemental carbon (EC) and equivalent black carbon (eBC), although EUSAAR2 protocol has been established and frequently used in EU for regulatory purposes. Discrepancies are observed due to thermal protocols used for OC/EC determinations and the effect of the chemical-physical properties of aerosol using optical measurements for eBC. In this work, a long-term inter-comparison of carbon measurements with two widely used protocols (EUSAAR2 and NIOSH870) was performed on PM

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.

Accurate misure di mercurio totale (HgT) nelle precipitazioni atmosferiche, raccolte in un'area suburbana di Cosenza (Calabria), nel periodo novembre 2013 - febbraio 2016, sono state eseguite per studiare la distribuzione delle concentrazioni di HgT e valutare il contributo mensile e stagionale dei flussi di Hg delle deposizioni umide. Un approccio metodologico simile era stato eseguito precedentemente in Calabria, su campioni di deposizioni atmosferiche, collezionate presso una stazione di monitoraggio del CNR in Sila.

Questo rapporto riassume i risultati ottenuti durante il progetto ECOMOBILITY - riguardo lo studio dell'impatto da traffico navale sul particolato atmosferico - nella città di Venezia. E' stato redatto in lingua italiana, con lo scopo di comunicare i risultati del progetto in modo più semplice ed immediato ad Autorità Portuale di Venezia (stakeholder del progetto) e al pubblico locale. SOMMARIO: 1. Introduzione; 2. Metodi utilizzati per l'elaborazione dei dati ad alta risoluzione; 3. Metodi utilizzati per l'elaborazione dei dati chimici; 4. Dati precedentemente disponibili a Venezia e Rijeka; 5. Discussione dei risultati; 5.1. Impatto da misure ad alta risoluzione; 5.2. Impatto da misure chimiche di vanadio.

Atmospheric particlulate matter (PM) is an heterogeneuous and dynamic mixture of particles with different origins, and its harmful effects are more strongly linked to its size and chemical composition than to its mass. The capability of some chemical compounds, present in airborne particulate matter, to generate reactive oxygen species (ROS) is known as “oxidative potential” (OP), and it represents a useful indicator of PM toxicity. The high production of ROS causes oxidative damages to cells that ultimately can lead to different chronic diseases. Although numerous studies were performed in the last years, however the biological mechanisms of toxicity and their relation with the chemical and physical properties of particulate matter are still largely unknown and futher research is need. In this work the oxidative potential of the water-soluble fraction of PM2.5 and PM10, collected at an urban background site in Southern Italy was investigated. The analysis of the OP were performed using the dithiothreitol (DTT) assay, a surrogate for cellular antioxidants, which analyses the rate of DTT depletion catalysed by chemical species present in the PM. Organic and Elemental carbon content was determined on all the collected samples in order to study the correlation between carbonaceous fractions and oxidative potential as well as to quantify the contribution of the combustion sources. DTT activity normalised by sampled air volume (OPV) and normalised by collected aerosol mass (OPM) were investigated. Results showed a seasonal trend in PM concentrations, in both size fractions, with larger concentrations during the cold seasons compared to the warm seasons. The same trend was also observed in carbonaceous faraction. OPV showed a similar trend with values larger in PM10 compared to PM2.5 as well as greater OPV values was observed in high carbon content samples. OPM was instead larger for PM2.5 than PM10. Also, OPV was well correlated both with mass concentration of PM and carbonaceous fractions, while no significant correlation has been observed with OPM

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.

Water soluble organic carbon significantly contributes to aerosol's carbon mass and its chemical composition is poorly characterized due to the huge number of species. In this study, we determined 94 water-soluble compounds: inorganic ions (Cl−, Br−, I−, NO3−, SO42−,K+, Mg+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2-C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free l - and d -amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The sampling was conducted using a micro-orifice uniform deposit impactor (MOUDI) at the urban area of Mestre-Venice from March to May 2016. The main aim of this work is to identify the source of each detected compound, evaluating its particle size distribution. Clear differences in size distributions were observed for each class of analyzed compounds. The positive matrix factorization (PMF) model was used to identify six factors related to different sources: a) primary biogenic aerosol particles with particle size > 10 μm; b) secondary sulfate contribution; c) biomass burning; d) primary biogenic aerosol particles distributed between 10 and 1 μm; e) an aged sea salt input and f) SOA pinene. Each factor was also characterized by different composition in waters soluble compounds and different particles size distribution.

Different power trained passenger cars were compared in a life cycle perspective (LCA) considering the Italian context for the year 2019. Main findings shows that battery electric vehicles, based on the current Italian energy mix, have the lower global warming emissions about 0.1 kgCO2eq/km. Lower particulate emissions of about 5x10-4 kgPM2,5eq/km and impact on human health about 7x10-7/km DALY were detected for petrol hybrid electric vehicles. Lower photochemical emissions of about 5x10-4 kgNMVOCeq/km were found for gasoline internal combustion engines vehicles.

In this study, the performance of two types of source apportionment models was evaluated by assessing the results provided by 40 different groups in the framework of an intercomparison organised by FAIRMODE WG3 (Forum for air quality modelling in Europe, Working Group 3). The evaluation was based on two performance indicators: z-scores and the root mean square error weighted by the reference uncertainty (RMSEu), with pre-established acceptability criteria. By involving models based on completely different and independent input data, such as receptor models (RMs) and chemical transport models (CTMs), the intercomparison provided a unique opportunity for their cross-validation. In addition, comparing the CTM chemical profiles with those measured directly at the source contributed to corroborate the consistency of the tested model results. The most commonly used RM was the US EPA- PMF version 5. RMs showed very good performance for the overall dataset (91% of z-scores accepted) while more difficulties were observed with the source contribution time series (72% of RMSEu accepted). Industrial activities proved to be the most difficult sources to be quantified by RMs, with high variability in the estimated contributions. In the CTMs, the sum of computed source contributions was lower than the measured gravimetric PM10 mass concentrations. The performance tests pointed out the differences between the two CTM approaches used for source apportionment in this study: brute force (or emission reduction impact) and tagged species methods. The sources meeting the z-score and RMSEu acceptability criteria tests were 50% and 86%, respectively. The CTM source contributions to PM10 were in the majority of cases lower than the RM averages for the corresponding source. The CTMs and RMs source contributions for the overall dataset were more comparable (83% of the z-scores accepted) than their time series (successful RMSEu in the range 25% - 34%). The comparability between CTMs and RMs varied depending on the source: traffic/exhaust and industry were the source categories with the best results in the RMSEu tests while the most critical ones were soil dust and road dust. The differences between RMs and CTMs source reconstructions confirmed the importance of cross validating the results of these two families of models. © 2019 The Authors, The authors warmly thank J. Vercauteren (VMM) for providing the CHEMKAR dataset. The CARA program was funded by the French Ministry of environment . IMT Lille Douai participates in the CaPPA project funded by the ANR through the PIA under contract ANR-11-LABX-0005-01 , the “Hauts de France” Regional Council and the European Regional Development Fund (ERDF). The C2TN/IST author gratefully acknowledges the FCT support through the UID/Multi/04349/2013 project. J.L. Jaffrezo would like to thank F. Donnaz, F. Masson, and S. Ngo for the chemical analyses of the Lens samples performed at IGE (ECOC, ions, sugars). These were possible on the Air-O-Sol analytical platform supported by Labex OSUG@2020 (ANR10 LABX56). A. Angyal was supported by National Research, Development and Innovation Office – NKFIH , contract number PD 125086 . H. Jorquera acknowledges support from Grant CONICYT/FONDAP/15110020. P . Thunis commented on an early version of the manuscript.

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.

Il contributo di ISAC-CNR previsto nella Convenzione di ricerca del 15/03/2016 tra ISAC-CNR e la Regione Puglia, rappresentata dal Responsabile Attuativo del Centro Salute Ambiente, prevede due linee di attività: 1) campagne di misura con AMS (High Resolution-Time of Flight-Aerosol Mass Spectrometer). 2) Misura delle concentrazioni e delle distribuzioni dimensionali del particolato atmosferico fine, ultrafine e delle nanoparticelle nell'area di Lecce La Convenzione prevedeva l'erogazione del 40% del contributo (importo totale pari a 70.000 euro) alla stipula della convenzione stessa. Per motivi non dipendenti da ISAC-CNR tale erogazione non è stata effettuata, pertanto le attività previste dall'accordo sono state espletate nelle parti e nei termini consentiti dalla disponibilità di fondi interni all'istituto stesso. Lo scopo di questo report è analizzare i risultati ottenuti nella fase di avvio dello studio relativamente alle due attività menzionate.

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.

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.

INDICE: Introduzione; Determinazione dei metalli nel PM10; Allegato: coordinate dei punti di prelievo dei campioni.

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.

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.

The analysis reported in this work has been performed to characterise PM10 concentration measured in an urban background site in Lecce (Apulia region, Italy). PM10 concentration and its inorganic chemical composition have been studied using three procedures: a qualitative analysis of the correlation coefficients between the different species and of the crustal enrichment factor; the cluster analysis (CA) and the principal component analysis (PCA). The results of the three procedures are in good agreement. The five groups identified by the CA correspond to the five principal components obtained with the PCA and they reflect the results qualitatively inferred using the two-species correlation coefficients. The CA results helped in putting in evidence a correlation between Ni, V and sulphate that was less evident in the PCA. The relative abundance of V is larger with wind from the N-NW directions where the main industrial sites of the region are located. This suggests the presence of anthropogenic inorganic secondary aerosol generated by a common source of V and SO2 that are likely the industrial releases and the ship emissions. The absolute PCA (APCA) allowed the quantitative apportionment of the five components observed: crustal matter (49.5%), secondary inorganic aerosol (24.1%), marine aerosol (6.3%), traffic (16.5%), and industrial (2.1%). Observed PM10 concentration clearly shows a seasonal pattern, opposite to the one observed in the northern and central Italy, with average PM10 larger in the warm season (spring and summer) with respect to the cold season as a consequence of the increase of crustal matter contribution likely due to the intrusion of African dust. These intrusions are more frequent in the warm season and have an influence on daily PM10 concentrations variable between 6% and 120% in this site. Correlation with meteorological data indicates that the more intense cases of intrusions of African dust happen with wind blowing from the SW direction. Average PM10 concentration decreases of about 23% during precipitation. The decrease is mainly due to the decrease in crustal matter contribution and secondary inorganic aerosol. The sum of the other three sources is almost not changing during precipitation.