Chemical characterization of atmospheric secondary organic aerosol of biogenic and anthropogenic origin

The main objective of this thesis was the chemical characterization of synthetic secondary organic aerosol (SOA) produced from atmospherically relevant anthropogenic and biogenic VOCs during reaction chamber experiments. In parallel, the resulting chemical features of these laboratory-SOA were used to interpret the composition of ambient samples of atmospheric fine particulate matter collected at several sites in Europe, in order to determine the fraction of ambient aerosol organic mass accounted for by biogenic and anthropogenic SOA.

Analisi del profilo tossicologico e cancerogeno del particolato atmosferico e identificazione dei rischi per la salute umana correlati all'esposizione

Gli impianti di incenerimento di rifiuti solidi suscitano preoccupazione nella popolazione per i possibili effetti avversi associati all’esposizione. Gli effetti delle polveri sottili (PM2.5), generate dai processi di combustione, sulla salute umana includono l’insorgenza di patologie a carico del sistema respiratorio e cardiovascolare e l’aumento della mortalità per malattie polmonari e probabilmente cancro al polmone. Lo scopo della tesi è quello di valutare il profilo tossicologico e cancerogeno del particolato atmosferico in prossimità dell’inceneritore di Bologna rispetto alle aree adiacenti mediante l’utilizzo di test alternativi alle metodologie in vivo, come il test di trasformazione cellulare e approcci di tossicogenomica (soprattutto trascrittomica) oltre alla valutazione della variazione del rischio cancerogeno indotto dall’esposizione di PM2.5 in diversi siti (massima ricaduta, controllo, fondo urbano e fondo rurale) e in differenti periodi di campionamento (estate 2008 e inverno 2009). Gli estratti di PM2.5 relativi alla stagione invernale sono risultati più tossici rispetto ai campioni estivi, che inducono tossicità soprattutto alle alte dosi. Per i campioni invernali il numero medio di colonie di cellule BALB/c 3T3 A31-1-1 risulta ridotto in modo significativo anche per le dosi più basse saggiate indipendentemente dal sito di provenienza. Tutti i campioni analizzati sono risultati negativi nel test di trasformazione cellulare in vitro. L’analisi dell’espressione genica delle cellule BALB/c 3T3 A31-1-1, in seguito all’esposizione agli estratti di PM2.5, ha mostrato un effetto stagionale evidente. Relativamente ai campioni invernali è stato evidenziato un maggior effetto tossico da parte del sito di controllo rispetto alla massima ricaduta, poiché nel sito di controllo risultano attivati marcatori di morte cellulare per apoptosi. La valutazione del rischio cancerogeno in tutti i siti valutati non mostra situazioni preoccupanti legate alla predizione di eccessi di rischio di tumori imputabili all’attività dell’inceneritore in quanto le stime di rischio non eccedono mai il valore limite riportato in letteratura.

Theoretical and Experimental Study of the Magnetic Separation of Pollutants from Wastewater

This Thesys reports the study of a HGMS (High GradientMagnetic Separation) process for the treatment of industrialwastewaters that considers an assisted chemical-physical pre-treatment for the removal of heavy metals through the bound by adsorption with added iron-oxide particulate matter (hematite). The considered filter, constituted by ferromagnetic stainless steel wool and permanent magnets, is studied with a new approach based on a statistical analysis that requires the study of the trajectories of the particles. Experimental activity on a laboratory device has been carried out in order to test the model.

Experimental and numerical analyses about the efficiency of flow through devices for the sediment controll in urban runoff

As land is developed, the impervious surfaces that are created increase the amount of runoff during rainfall events, disrupting the natural hydrologic cycle, with an increment in volume of runoff and in pollutant loadings. Pollutants deposited or derived from an activity on the land surface will likely end up in stormwater runoff in some concentration, such as nutrients, sediment, heavy metals, hydrocarbons, gasoline additives, pathogens, deicers, herbicides and pesticides. Several of these pollutants are particulate-bound, so it appears clear that sediment removal can provide significant water-quality improvements and it appears to be important the knowledge of the ability of stromwater treatment devices to retain particulate matter. For this reason three different units which remove sediments have been tested through laboratory. In particular a roadside gully pot has been tested under steady hydraulic conditions, varying the characteristics of the influent solids (diameter, particle size distribution and specific gravity). The efficiency in terms of particles retained has been evaluated as a function of influent flow rate and particles characteristics; results have been compared to efficiency evaluated applying an overflow rate model. Furthermore the role of particles settling velocity in efficiency determination has been investigated. After the experimental runs on the gully pot, a standard full-scale model of an hydrodynamic separator (HS) has been tested under unsteady influent flow rate condition, and constant solid concentration at the input. The results presented in this study illustrate that particle separation efficiency of the unit is predominately influenced by operating flow rate, which strongly affects the particles and hydraulic residence time of the system. The efficiency data have been compared to results obtained from a modified overflow rate model; moreover the residence time distribution has been experimentally determined through tracer analyses for several steady flow rates. Finally three testing experiments have been performed for two different configurations of a full-scale model of a clarifier (linear and crenulated) under unsteady influent flow rate condition, and constant solid concentration at the input. The results illustrate that particle separation efficiency of the unit is predominately influenced by the configuration of the unit itself. Turbidity measures have been used to compare turbidity with the suspended sediments concentration, in order to find a correlation between these two values, which can allow to have a measure of the sediments concentration simply installing a turbidity probe.

Quantifying and modeling ecosystem services provided by urban greening in cities of the Southern Alps, N Italy

Population growth in urban areas is a world-wide phenomenon. According to a recent United Nations report, over half of the world now lives in cities. Numerous health and environmental issues arise from this unprecedented urbanization. Recent studies have demonstrated the effectiveness of urban green spaces and the role they play in improving both the aesthetics and the quality of life of its residents. In particular, urban green spaces provide ecosystem services such as: urban air quality improvement by removing pollutants that can cause serious health problems, carbon storage, carbon sequestration and climate regulation through shading and evapotranspiration. Furthermore, epidemiological studies with controlled age, sex, marital and socio-economic status, have provided evidence of a positive relationship between green space and the life expectancy of senior citizens. However, there is little information on the role of public green spaces in mid-sized cities in northern Italy. To address this need, a study was conducted to assess the ecosystem services of urban green spaces in the city of Bolzano, South Tyrol, Italy. In particular, we quantified the cooling effect of urban trees and the hourly amount of pollution removed by the urban forest. The information was gathered using field data collected through local hourly air pollution readings, tree inventory and simulation models. During the study we quantified pollution removal for ozone, nitrogen dioxide, carbon monoxide and particulate matter (<10 microns). We estimated the above ground carbon stored and annually sequestered by the urban forest. Results have been compared to transportation CO2 emissions to determine the CO2 offset potential of urban streetscapes. Furthermore, we assessed commonly used methods for estimating carbon stored and sequestered by urban trees in the city of Bolzano. We also quantified ecosystem disservices such as hourly urban forest volatile organic compound emissions.

Chemistry of aerosol particles and fog droplets during fall-winter season in the Po Valley

Air quality represents a key issue in the so-called pollution “hot spots”: environments in which anthropogenic sources are concentrated and dispersion of pollutants is limited. One of these environments, the Po Valley, normally experiences exceedances of PM10 and PM2.5 concentration limits, especially in winter when the ventilation of the lower layers of the atmosphere is reduced. This thesis provides a highlight of the chemical properties of particulate matter and fog droplets in the Po Valley during the cold season, when fog occurrence is very frequent. Fog-particles interactions were investigated with the aim to determine their impact on the regional air quality. Size-segregated aerosol samples were collected in Bologna, urban site, and San Pietro Capofiume (SPC), rural site, during two campaigns (November 2011; February 2013) in the frame of Supersito project. The comparison between particles size-distribution and chemical composition in both sites showed the relevant contribution of the regional background and secondary processes in determining the Po Valley aerosol concentration. Occurrence of fog in November 2011 campaign in SPC allowed to investigate the role of fog formation and fog chemistry in the formation, processing and deposition of PM10. Nucleation scavenging was investigated with relation to the size and the chemical composition of particles. We found that PM1 concentration is reduced up to 60% because of fog scavenging. Furthermore, aqueous-phase secondary aerosol formation mechanisms were investigated through time-resolved measurements. In SPC fog samples have been systematically collected and analysed since the nineties; a 20 years long database has been assembled. This thesis reports for the first time the results of this long time series of measurements, showing a decrease of sulphate and nitrate concentration and an increase of pH that reached values close to neutrality. A detailed discussion about the occurred changes in fog water composition over two decades is presented.

Origin and variability of PM10 and atmospheric radiotracers at the WMO-GAW station of Mt. Cimone (1998-2011) and in the central Po Valley

Particulate matter is one of the main atmospheric pollutants, with a great chemical-environmental relevance. Improving knowledge of the sources of particulate matter and of their apportionment is needed to handle and fulfill the legislation regarding this pollutant, to support further development of air policy as well as air pollution management. Various instruments have been used to understand the sources of particulate matter and atmospheric radiotracers at the site of Mt. Cimone (44.18° N, 10.7° E, 2165 m asl), hosting a global WMO-GAW station. Thanks to its characteristics, this location is suitable investigate the regional and long-range transport of polluted air masses on the background Southern-Europe free-troposphere. In particular, PM10 data sampled at the station in the period 1998-2011 were analyzed in the framework of the main meteorological and territorial features. A receptor model based on back trajectories was applied to study the source regions of particulate matter. Simultaneous measurements of atmospheric radionuclides Pb-210 and Be-7 acquired together with PM10 have also been analysed to acquire a better understanding of vertical and horizontal transports able to affect atmospheric composition. Seasonal variations of atmospheric radiotracers have been studied both analysing the long-term time series acquired at the measurement site as well as by means of a state-of-the-art global 3-D chemistry and transport model. Advection patterns characterizing the circulation at the site have been identified by means of clusters of back-trajectories. Finally, the results of a source apportionment study of particulate matter carried on in a midsize town of the Po Valley (actually recognised as one of the most polluted European regions) are reported. An approach exploiting different techniques, and in particular different kinds of models, successfully achieved a characterization of the processes/sources of particulate matter at the two sites, and of atmospheric radiotracers at the site of Mt. Cimone.