Inter-annual trends of ultrafine particles in urban Europe.

Ultrafine particles (UFP, those with diameters ≤ 100 nm), have been reported to potentially penetrate deeply into the respiratory system, translocate through the alveoli, and affect various organs, potentially correlating with increased mortality. The aim of this study is to assess long-term trends (5-11 years) in mostly urban UFP concentrations based on measurements of particle number size distributions (PNSD). Additionally, concentrations of other pollutants and meteorological variables were evaluated to support the interpretations. PNSD datasets from 12 urban background (UB), 5 traffic (TR), 3 suburban background (SUB) and 1 regional background (RB) sites in 15 European cities and 1 in the USA were evaluated. The non-parametric Theil-Sen's method was used to detect monotonic trends. Meta-analyses were carried out to assess the overall trends and those for different environments. The results showed significant decreases in NO, NO2, BC, CO, and particle concentrations in the Aitken (25-100 nm) and the Accumulation (100-800 nm) modes, suggesting a positive impact of the implementation of EURO 5/V and 6/VI vehicle standards on European air quality. The growing use of Diesel Particle Filters (DPFs) might also have clearly reduced exhaust emissions of BC, PM, and the Aitken and Accumulation mode particles. However, as reported by prior studies, there remains an issue of poor control of Nucleation mode particles (smaller than 25 nm), which are not fully reduced with current DPFs, without emission controls for semi-volatile organic compounds, and might have different origins than road traffic. Thus, contrasting trends for Nucleation mode particles were obtained across the cities studied. This mode also affected the UFP and total PNC trends because of the high proportion of Nucleation mode particles in both concentration ranges. It was also found that the urban temperature increasing trends might have also influenced those of PNC, Nucleation and Aitken modes.

Size-Resolved Redox Activity and Cytotoxicity of Water-Soluble Urban Atmospheric Particulate Matter: Assessing Contributions from Chemical Components.

Throughout the cold and the warm periods of 2020, chemical and toxicological characterization of the water-soluble fraction of size segregated particulate matter (PM) (<0.49, 0.49−0.95, 0.95−1.5, 1.5−3.0, 3.0−7.2 and >7.2 µm) was conducted in the urban agglomeration of Thessaloniki, northern Greece. Chemical analysis of the water-soluble PM fraction included water-soluble organic carbon (WSOC), humic-like substances (HULIS), and trace elements (V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd and Pb). The bulk (sum of all size fractions) concentrations of HULIS were 2.5 ± 0.5 and 1.2 ± 0.3 µg m−3, for the cold and warm sampling periods, respectively with highest values in the <0.49 µm particle size fraction. The total HULIS-C/WSOC ratio ranged from 17 to 26% for all sampling periods, confirming that HULIS are a significant part of WSOC. The most abundant water-soluble metals were Fe, Zn, Cu, and Mn. The oxidative PM activity was measured abiotically using the dithiothreitol (DTT) assay. In vitro cytotoxic responses were investigated using mitochondrial dehydrogenase (MTT). A significant positive correlation was found between OPmDTT, WSOC, HULIS and the MTT cytotoxicity of PM. Multiple Linear Regression (MLR) showed a good relationship between OPMDTT, HULIS and Cu.

Characterisation of the correlations between oxidative potential and in vitro biological effects of PM10 at three sites in the central Mediterranean.

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.

Concentration and size distribution of atmospheric particles in southern Italy during COVID-19 lockdown period.

Many countries imposed lockdown (LD) to limit the spread of COVID-19, which led to a reduction in the emission of anthropogenic atmospheric pollutants. Several studies have investigated the effects of LD on air quality, mostly in urban settings and criteria pollutants. However, less information is available on background sites, and virtually no information is available on particle number size distribution (PNSD). This study investigated the effect of LD on air quality at an urban background site representing a near coast area in the central Mediterranean. The analysis focused on equivalent black carbon (eBC), particle mass concentrations in different size fractions: PM2.5 (aerodynamic diameter Da < 2.5 µm), PM10 (Da < 10 µm), PM10-2.5 (2.5 < Da < 10 µm); and PNSD in a wide range of diameters (0.01-10 µm). Measurements in 2020 during the national LD in Italy and period immediately after LD (POST-LD period) were compared with those in the corresponding periods from 2015 to 2019. The results showed that LD reduced the frequency and intensity of high-pollution events. Reductions were more relevant during POST-LD than during LD period for all variables, except quasi-ultrafine particles and PM10-2.5. Two events of long-range transport of dust were observed, which need to be identified and removed to determine the effect of LD. The decreases in the quasi-ultrafine particles and eBC concentrations were 20%, and 15-22%, respectively. PM2.5 concentration was reduced by 13-44% whereas PM10-2.5 concentration was unaffected. The concentration of accumulation mode particles followed the behaviour of PM2.5, with reductions of 19-57%. The results obtained could be relevant for future strategies aimed at improving air quality and understanding the processes that influence the number and mass particle size distributions.

Characterization of fresh PM deposits on calcareous stone surfaces: Seasonality, source apportionment and soiling potential.

Particulate matter (PM) pollution is one of the major threats to cultural heritage outdoors. It has been recently implied that organic aerosols will prevail over inorganic carbon particulates in the future, changing the main mechanisms of damage caused by poor air quality to calcareous heritage in particular. We studied fresh particulate deposits on marble and limestone surfaces exposed to urban air in sheltered and unsheltered configurations. Due to different air pollution sources in different seasons, the amount and composition of surface deposits varied throughout the year. The main and most constant contributor to PM2.5 (particles smaller than 2.5 µm) were primary traffic emissions (30 %), followed by secondary formation of acidic inorganic aerosols, such as sulphate in summer and nitrate in winter (33 % altogether), and seasonal biomass-burning emissions (14 %). Although biomass burning is the major source of primary organic aerosols including the light-absorbing fraction that prevailed over black carbon (BC) in colder months (up to 60 % carbonaceous aerosol mass), we show that surface darkening causing the soiling effect is still governed by the minor BC fraction of atmospheric aerosols, which remained below 20 % of the carbonaceous aerosol mass throughout the year. This, however, can change in remote environments affected by biomass-burning emissions, such as winter resorts, or by rigorous BC mitigation measures in the future. In the short run, sheltered positions were less affected by different removal processes, but we show that surface deposits are not simply additive when considering longer periods of time. This must be taken into account when extrapolating surface accumulation to longer time scales.

Inter-annual variability of source contributions to PM10, PM2.5, and oxidative potential in an urban background site in the central mediterranean.

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 0.39 nmol/min·m3 in PM10 and 0.29 in PM2.5 nmol/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 < 0.05) to the oxidative potential of each size fraction. Inter-annual trends were more evident on PM2.5 with reductions of biomass burning contribution and increases in traffic contribution in the 2016-2017 period. Crustal contributions were similar for the two periods, in both size fractions. Carbonates were comparable in PM10 with a slight increase in PM2.5. Sea spray decreased in PM10. The DTTV of PM2.5 peaked during cold periods, while, the DTTV of the PM10-2.5 fraction peaked in summer, suggesting that different sources, with different seasonality, influence OP in the PM2.5 and PM10-2.5 fractions. Analysis showed that sea spray, crustal, and carbonates sources contribute ∼13.6% to DTTV in PM2.5 and ∼62.4% to DTTV in PM10-2.5. Combustion sources (biomass burning and traffic) contribute to the majority of DTTV (50.6%) in PM2.5 and contribute for ∼26% to DTTV in PM10-2.5. Secondary nitrate contributes to DTTV in both fine and coarse fraction; secondary sulphate contribute to DTTV in PM2.5 with negligible contributions to DTTV in PM10-2.5.

Development and characterization of a gold nanoparticles glassy carbon modified electrode for dithiotreitol (DTT) detection suitable to be applied for determination of atmospheric particulate oxidative potential.

A gold nanostructured electrochemical sensor based on modified GC electrode for thiols' detection is described and characterized. This sensor is a suitable device for the measurement of the oxidative potential (OP) of the atmospheric particulate matter (PM), considered a global indicator of adverse health effects of PM, as an alternative to the classic spectrophotometric methods. The operating principle is the determination of the OP, through the measurement of the consumption of DTT content. The DTT-based chemical reactivity is indeed a quantitative acellular probe for assessment of the capacity of the atmospheric PM to catalyze reactive oxygen species generation which contributes to the induction of oxidative stress in living organisms and in turn to the outcome of adverse health effects. To make the sensors, glassy carbon electrodes, traditional (GC) and screen printed (SPE) electrodes, have been electrochemically modified with well-shaped rounded gold nanoparticles (AuNPs) by using a deposition method that allows obtaining a stable and efficient modified surface in a very simple and reproducible modality. The chemical and morphological characterization of the nano-hybrid material has been performed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy coupled with electron dispersive spectroscopy analysis (SEM/EDS). The electrochemical properties have been evaluated by cyclic voltammetry (CV) and chrono-amperometry (CA) in phosphate buffer at neutral pH as requested in DTT assay for OP measurements. The electroanalytical performances of the sensor in DTT detection are strongly encouraging showing low LODs (0.750 µM and 1.5 µM), high sensitivity (0.0622 µA cm-2 µM-1 and 0.0281 µA cm-2 µM-1), wide linear and dynamic ranges extending over 2-4 orders of magnitude and high selectivity. FIA preliminary results obtained on measuring the DTT rate consumption in six PM aqueous extracts samples showed a good correlation with measurements obtained in parallel on the same set of samples by using the classic spectrophotometric method based on the Ellman's reactive use. These results confirm the high selectivity of the method and its suitability for application to be applied in PM oxidative potential measurements.

Role of air pollutants mediated oxidative stress in respiratory diseases.

Airborne particulate (PM) components from fossil fuel combustion can induce oxidative stress initiated by reactive oxygen species (ROS) that are strongly correlated with airway inflammation and asthma. A valid biomarker of airway inflammation is fractionated exhaled nitric oxide (FENO). The oxidative potential of PM2.5 can be evaluated with the dithiothreitol (DTT) dosage, which represents both ROS chemically produced and intracellular ROS of macrophages. This correlates with quality indicators of the internal environment and ventilation strategies such as dilution and removal of airborne contaminants.

Chemical characterisation of PM10 from ship emissions: a study on samples from hydrofoil exhaust stacks.

A chemical characterization of PM10 collected at hydrofoil exhaust stacks was performed conducting two on-board measuring campaigns, with the aim of assessing the ship emission impact on PM10 collected in the coastal area of Naples (Southern Italy) and providing information about the characteristics of this important PM emission source.Samples were analysed determining the contribution of different chemical parameters to PM10's mass, which consisted of polycyclic aromatic hydrocarbons (PAHs) (0.10 ± 0.12%), total carbon (61.9% ± 20.0%, with 40.4% of organic carbon, OC, and 21.5% of elemental carbon, EC) and elemental fraction (0.44% ± 1.00%). Differences in terms of composition and chemical parameter profiles were observed between samples collected during offshore navigation (Off) and samples collected during shunting operations (SO), the latter of higher concern on a local scale. For SO samples, lower contributions of OC and EC were observed (39.7% and 19.6% respectively) compared to Off samples (41.5% and 24.2%), and an increase in terms of elements (from 0.32 to 0.51%) and PAHs (from 0.06 to 0.12%) concentrations was observed. In addition, enrichment factors (EFs) for some elements such as V, Zn, Cd, Cu, Ag and Hg as well as PAHs profile varied significantly between SO and Off. Data presented here were compared with data on chemical composition of PM10 sampled in a tunnel, in a background site and in an urban site in the city of Naples. Results indicated that shipping activities contributed significantly to the emission of V and, in some extent, Zn and Cd; in addition, PAH profiles indicated a greater contribution to urban PM10 from vehicular traffic than shipping emissions. These results can significantly contribute to the correct evaluation of the influence of shipping emission on PM10 generation in urban coastal areas and can be a useful reference for similar studies. The coastal area of Naples is an important example of the coexistence of residential, touristic and natural areas with pollutants emission sources including, among the others, shipping emissions. In this and similar contexts, it is important to distinguish the contribution of each emission source to clearly define environmental control policies.

A review on measurements of SARS-CoV-2 genetic material in air in outdoor and indoor environments: Implication for airborne transmission.

Airborne transmission of SARS-CoV-2 has been object of debate in the scientific community since the beginning of COVID-19 pandemic. This mechanism of transmission could arise from virus-laden aerosol released by infected individuals and it is influenced by several factors. Among these, the concentration and size distribution of virus-laden particles play an important role. The knowledge regarding aerosol transmission increases as new evidence is collected in different studies, even if it is not yet available a standard protocol regarding air sampling and analysis, which can create difficulties in the interpretation and application of results. This work reports a systematic review of current knowledge gained by 73 published papers on experimental determination of SARS-CoV-2 RNA in air comparing different environments: outdoors, indoor hospitals and healthcare settings, and public community indoors. Selected papers furnished 77 datasets: outdoor studies (9/77, 11.7%) and indoor studies (68/77. 88.3%). The indoor datasets in hospitals were the vast majority (58/68, 85.3%), and the remaining (10/68, 14.7%) were classified as community indoors. The fraction of studies having positive samples, as well as positivity rates (i.e. ratios between positive and total samples) are significantly larger in hospitals compared to the other typologies of sites. Contamination of surfaces was more frequent (in indoor datasets) compared to contamination of air samples; however, the average positivity rate was lower compared to that of air. Concentrations of SARS-CoV-2 RNA in air were highly variables and, on average, lower in outdoors compared to indoors. Among indoors, concentrations in community indoors appear to be lower than those in hospitals and healthcare settings.

Airborne concentrations of SARS-CoV-2 in indoor community environments in Italy.

COVID-19 pandemic raised a debate regarding the role of airborne transmission. Information regarding virus-laden aerosol concentrations is still scarce in community indoors and what are the risks for general public and the efficiency of restriction policies. This work investigates, for the first time in Italy, the presence of SARS-CoV-2 RNA in air samples collected in different community indoors (one train station, two food markets, one canteen, one shopping centre, one hair salon, and one pharmacy) in three Italian cities: metropolitan city of Venice (NE of Italy), Bologna (central Italy), and Lecce (SE of Italy). Air samples were collected during the maximum spread of the second wave of pandemic in Italy (November and December 2020). All collected samples tested negative for the presence of SARS-CoV-2, using both real-time RT-PCR and ddPCR, and no significant differences were observed comparing samples taken with and without customers. Modelling average concentrations, using influx of customers' data and local epidemiological information, indicated low values (i.e. < 0.8 copies m-3 when cotton facemasks are used and even lower for surgical facemasks). The results, even if with some limitations, suggest that the restrictive policies enforced could effectively reduce the risk of airborne transmissions in the community indoor investigated, providing that physical distance is respected.

Characterization of airborne particulate fractions from the port city of Rijeka, Croatia.

The aim of this work was characterization of airborne particulates in the port city of Rijeka in order to evaluate impact of ship emissions on air quality. Samples of airborne particulates were collected with a ten stages cascade impactor during two campaigns: autumn and spring. A total of 16 weekly samples were analyzed on mass concentration, ions, metals and carbonaceous species (EC, OC, WSOC). Distribution of airborne fractions showed a bimodal distribution, with two maxima: one in coarse, and other in fine fraction. Source apportionment using PMF receptor model identified six sources of airborne particulates in Rijeka: crustal, biomass burning, sea salt, traffic/metal industry, combustion/SIA and HFO burning, i.e., ship emission (contribution 3%). The contribution of ship traffic to primary emission of particulate matter, using vanadium as tracer, indicated a twofold increase for PM10 and PM2.5 relative to 2012-14. An unusual desert dust event was registered in autumn campaign.

On the concentration of SARS-CoV-2 in outdoor air and the interaction with pre-existing atmospheric particles.

The spread of SARS-CoV-2 by contact (direct or indirect) is widely accepted, but the relative importance of airborne transmission is still controversial. Probability of outdoor airborne transmission depends on several parameters, still rather uncertain: virus-laden aerosol concentrations, viability and lifetime, minimum dose necessary to transmit the disease. In this work, an estimate of outdoor concentrations in northern Italy (region Lombardia) was performed using a simple box model approach, based on an estimate of respiratory emissions, with a specific focus for the cities of Milan and Bergamo (Italy). In addition, the probability of interaction of virus-laden aerosol with pre-existing particles of different sizes was investigated. Results indicate very low (<1 RNA copy/m3) average outdoor concentrations in public area, excluding crowded zones, even in the worst case scenario and assuming a number of infects up to 25% of population. On average, assuming a number of infects equal to 10% of the population, the time necessary to inspire a quantum (i.e. the dose of airborne droplet nuclei required to cause infection in 63% of susceptible persons) would be 31.5 days in Milan (range 2.7-91 days) and 51.2 days in Bergamo (range 4.4-149 days). Therefore, the probability of airborne transmission due to respiratory aerosol is very low in outdoor conditions, even if it could be more relevant for community indoor environments, in which further studies are necessary to investigate the potential risks. We theoretically examined if atmospheric particles can scavenge virus aerosol, through inertial impact, interception, and Brownian diffusion. The probability was very low. In addition, the probability of coagulation of virus-laden aerosol with pre-existing atmospheric particles resulted negligible for accumulation and coarse mode particles, but virus-laden aerosol could act as sink of ultrafine particles (around 0.01 µm in diameter). However, this will not change significantly the dynamics behaviour of the virus particle or its permanence time in atmosphere.

What impact of air pollution in pediatric respiratory allergic diseases.

Respiratory allergies are known to affect people all over the world. Environmental factors related to pollution play a significant etiopathogenic role in this regard. Polluting sources are industrial activities and urban traffic, capable of generating various types of pollutants that trigger inflammatory, direct, and indirect damage to tissues, promoting allergic symptoms, even serious ones, and interfering with the pharmacologic response. They are also able to modify pollen, promoting allergic sensitization. Pollution could have played a significant predisposing role in the ongoing morbidity and mortality of SARS-CoV-2.

Inter-comparison of carbon content in PM10 and PM2.5 measured with two thermo-optical protocols on samples collected in a Mediterranean site.

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.

Size-resolved particle emission factors of vehicular traffic derived from urban eddy covariance measurements.

Road traffic is one of the major sources of atmospheric particles in urban areas. Modelling the contribution of this source to urban pollution requires reliable estimates of emission factors possibly resolved in size. In this work, size-resolved particle emission factors (EFs) of the mixed vehicle fleet were measured in the urban area of Lecce (south-eastern Italy). The approach used is based on vertical fluxes measured with eddy-covariance, counting of vehicles, and estimation of footprints. Results show that the average EF in number (range 0.009-3 µm) was 2.2*1014 #/Veh km, being dominated by ultrafine particles (Dp < 0.25 µm) due to exhaust emissions. EF number size distribution decreases with particle size. A reduction of more than four orders of magnitude was observed at Dp ≅ 0.9 µm. EF mass size distribution reaches a maximum around Dp ≅ 0.3 µm then decreases until Dp ≅ 0.9 µm. For larger particles EF in mass increases for the influence of non-exhaust emissions. Average emission factor of PM1 was 56 mg/Veh Km and that of PM2.5 was 63 mg/Veh Km. A comparison of measurements taken in 2010 and 2015 in the same area shows a decreasing trend of the average total EF in number of about 56%, likely as a consequence of the increased use of new generation vehicles following more restrictive limits for particle emissions.

Characterization of the water soluble fraction in ultrafine, fine, and coarse atmospheric aerosol.

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.

Characterisation of particle size distributions and corresponding size-segregated turbulent fluxes simultaneously with CO2 exchange in an urban area.

Number and mass particle concentrations and fluxes were measured, simultaneously with CO2 concentration and flux, in the urban area of Lecce (Italy). The measurements of the turbulent exchanges of atmospheric particles and gas were performed with an eddy-covariance station located near the busiest road of the town. For the smaller particles, the diurnal evolution of the particle number concentrations and fluxes shows a clear correlation with human activities, in particular vehicular traffic, which is the obvious candidate as the source of the two clear peaks in the CPC concentration in the morning and in the evening. The fluxes were upward for all the measurement period, even though small net deposition was observed for larger particles and during weekend. For the CPC, the correlation with the traffic daily pattern is extremely strong. The city is a continuous particle source. The data analysis seems also to suggest the presence of local urban nucleation events. CO2 and particle concentrations were larger at low wind velocity, instead, fluxes were larger at high wind velocity. This opposite behaviour suggests that the influence of local urban emissions is larger on fluxes with respect to concentrations. The average daily patterns of CO2 concentration show an overlap between biogenic cycle and urban emissions. Again, traffic appears to be the dominant source for fluxes and the urban area is a net source of CO2.

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

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