In this work, new tools in atmospheric pollutant sampling and analysis were applied in order to go deeper in source apportionment study. The project was developed mainly by the study of atmospheric emission sources in a suburban area influenced by a municipal solid waste incinerator (MSWI), a medium-sized coastal tourist town and a motorway. Two main research lines were followed. For what concerns the first line, the potentiality of the use of PM samplers coupled with a wind select sensor was assessed. Results showed that they may be a valid support in source apportionment studies. However, meteorological and territorial conditions could strongly affect the results. Moreover, new markers were investigated, particularly focusing on the processes of biomass burning. OC revealed a good biomass combustion process indicator, as well as all determined organic compounds. Among metals, lead and aluminium are well related to the biomass combustion. Surprisingly PM was not enriched of potassium during bonfire event. The second research line consists on the application of Positive Matrix factorization (PMF), a new statistical tool in data analysis. This new technique was applied to datasets which refer to different time resolution data. PMF application to atmospheric deposition fluxes identified six main sources affecting the area. The incinerator’s relative contribution seemed to be negligible. PMF analysis was then applied to PM2.5 collected with samplers coupled with a wind select sensor. The higher number of determined environmental indicators allowed to obtain more detailed results on the sources affecting the area. Vehicular traffic revealed the source of greatest concern for the study area. Also in this case, incinerator’s relative contribution seemed to be negligible. Finally, the application of PMF analysis to hourly aerosol data demonstrated that the higher the temporal resolution of the data was, the more the source profiles were close to the real one.

In this thesis, new advances in the development of spectroscopic based methods for the characterization of heritage materials have been achieved. As concern FTIR spectroscopy new approaches aimed at exploiting near and far IR region for the characterization of inorganic or organic materials have been tested. Paint cross-section have been analysed by FTIR spectroscopy in the NIR range and an “ad hoc” chemometric approach has been developed for the elaboration of hyperspectral maps. Moreover, a new method for the characterization of calcite based on the use of grinding curves has been set up both in MIR and in FAR region. Indeed, calcite is a material widely applied in cultural heritage, and this spectroscopic approach is an efficient and rapid tool to distinguish between different calcite samples. Different enhanced vibrational techniques for the characterisation of dyed fibres have been tested. First a SEIRA (Surface Enhanced Infra-Red Absorption) protocol has been optimised allowing the analysis of colorant micro-extracts thanks to the enhancement produced by the addition of gold nanoparticles. These preliminary studies permitted to identify a new enhanced FTIR method, named ATR/RAIRS, which allowed to reach lower detection limits. Regarding Raman microscopy, the research followed two lines, which have in common the aim of avoiding the use of colloidal solutions. AgI based supports obtained after deposition on a gold-coated glass slides have been developed and tested spotting colorant solutions. A SERS spectrum can be obtained thanks to the photoreduction, which the laser may induce on the silver salt. Moreover, these supports can be used for the TLC separation of a mixture of colorants and the analyses by means of both Raman/SERS and ATR-RAIRS can be successfully reached. Finally, a photoreduction method for the “on fiber” analysis of colorant without the need of any extraction have been optimised.

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.

MFA and LCA methodologies were applied to analyse the anthropogenic aluminium cycle in Italy with focus on historical evolution of stocks and flows of the metal, embodied GHG emissions, and potentials from recycling to provide key features to Italy for prioritizing industrial policy toward low-carbon technologies and materials. Historical trend series were collected from 1947 to 2009 and balanced with data from production, manufacturing and waste management of aluminium-containing products, using a ‘top-down’ approach to quantify the contemporary in-use stock of the metal, and helping to identify ‘applications where aluminium is not yet being recycled to its full potential and to identify present and future recycling flows’. The MFA results were used as a basis for the LCA aimed at evaluating the carbon footprint evolution, from primary and electrical energy, the smelting process and the transportation, embodied in the Italian aluminium. A discussion about how the main factors, according to the Kaya Identity equation, they did influence the Italian GHG emissions pattern over time, and which are the levers to mitigate it, it has been also reported. The contemporary anthropogenic reservoirs of aluminium was estimated at about 320 kg per capita, mainly embedded within the transportation and building and construction sectors. Cumulative in-use stock represents approximately 11 years of supply at current usage rates (about 20 Mt versus 1.7 Mt/year), and it would imply a potential of about 160 Mt of CO2eq emissions savings. A discussion of criticality related to aluminium waste recovery from the transportation and the containers and packaging sectors was also included in the study, providing an example for how MFA and LCA may support decision-making at sectorial or regional level. The research constitutes the first attempt of an integrated approach between MFA and LCA applied to the aluminium cycle in Italy.

La caratterizzazione di sedimenti contaminati è un problema complesso, in questo lavoro ci si è occupati di individuare una metodologia di caratterizzazione che tenesse conto sia delle caratteristiche della contaminazione, con analisi volte a determinare il contenuto totale di contaminanti, sia della mobilità degli inquinanti stessi. Una adeguata strategia di caratterizzazione può essere applicata per la valutazione di trattamenti di bonifica, a questo scopo si è valutato il trattamento di soil washing, andando ad indagare le caratteristiche dei sedimenti dragati e del materiale in uscita dal processo, sabbie e frazione fine, andando inoltre a confrontare le caratteristiche della sabbia in uscita con quelle delle sabbie comunemente usate per diverse applicazioni. Si è ritenuto necessario indagare la compatibilità dal punto di vista chimico, granulometrico e morfologico. Per indagare la mobilità si è scelto di applicare i test di cessione definiti sia a livello internazionale che italiano (UNI) e quindi si sono sviluppate le tecnologie necessarie alla effettuazione di test di cessione in modo efficace, automatizzando la gestione del test a pHstat UNI CEN 14997. Questo si è reso necessario a causa della difficoltà di gestire il test manualmente, per via delle tempistiche difficilmente attuabili da parte di un operatore. Le condizioni redox influenzano la mobilità degli inquinanti, in particolare l’invecchiamento all’aria di sedimenti anossici provoca variazioni sensibili nello stato d’ossidazione di alcune componenti, incrementandone la mobilità, si tratta quindi di un aspetto da considerare quando si individuano le adeguate condizioni di stoccaggio-smaltimento, si è eseguita a questo scopo una campagna sperimentale. / The characterization of contaminated sediments is a daedalean problem , in this paper the focus is to identify a method of characterization that takes into account both the characteristics of the contamination, with analysis to determine the total content of contaminants, and the mobility of the pollutants themselves. An adequate characterization strategy can be applied for the evaluation of managing options, and treatments of reclamation, for this purpose , it is assessed the treatment of soil washing, taking account of the characteristics of the sediment and dredged material in the process output, sands and fine fraction, and also to comparing the characteristics of the sand in output with those of sands commonly used for different applications. It was considered necessary to investigate the compatibility from the chemical point of view, particle size and morphology. Different leaching test have been applied to investigate the mobility, they are defined in the international and Italian norms (UNI) and therefore have developed the technologies necessary to carry out tests of the sale effectively, automating the management of test pHStat CEN 14997. That has been helpful due to the type of test, which is difficult to handle in manual way. The redox conditions affect the mobility of pollutants , in particular the aging of anoxic sediments in air causes substantial changes in the oxidation state of some components , increasing mobility , it is therefore an aspect to be considered when identifying the appropriate conditions storage - disposal. With that goal a series of experiments have been carried out.

Univ., Diss.--Fribourg (Suisse), 1994.

Les processus de déformation contrôlant l'amincissement de la lithosphère continentale sont encoremal contraints. Nos connaissances sont principalement basées sur la modélisation thermomécaniqued'extension à l'échelle de la lithosphere—utilisant des lois rhéologiques derivées expérimentalement,l'imagerie géophysique et l'analyse de xénolithes provenant de rift continentaux actifs à ce jour, tels quele Rift Est-Africain. L'originalité de ce travail reside dans l'étude des deux plus grands massifs depéridotites sous-continentales ayant enregistrées des conditions primaires du facies à diamant: lesmassifs de Beni Bousera au nord du Maroc et de Ronda au sud de l'Espagne, respectivement. Lesstructures et la zonation petrologique et métamorphique —impliquant une évolution polybarique etpolythermique— préservéees dans ces massifs offrent une opportunité unique pour étudier l'évolutionthermo-mécanique du manteau sous-continental dans un contexte extensif.Dans ce travail, nous avons étudié les mécanismes de déformation des péridotites et despyroxénites afin de contraindre les modes d'exhumation du manteau lithosphérique sous-continental,depuis des conditions du facies des lherzolites à grenat, jusqu'au facies à spinelle et enfin à plagioclase.Nous avons combiné la cartographie des faciès tectono-métamorphiques et des structures ductiles dedéformation, l'analyse des microstructures, la mesure d'orientations préférentielles de réseau (OPR), etla géothermobarométrie conventionelle couplée à la modélisation thermodynamique (PerpleX) afin decontraindre les conditions de pression et température de la déformation. Nous avons montré quel'exhumation précoce du facies à grenat au facies à spinelle était accomodée par une faille transtensiveaffectant le manteau lithosphérique. Dans ce contexte, la zonation tectono-métamorphique et legradient thermique important (ca. 100ºC/km) préservés à Beni Bousera résultent de la juxtapositionmécanique de domaines lithosphériques initialement équilibrés à différentes pressions et températures,fossilisée à une profondeur de ca. 60 km durant l'Oligocène supérieur (ca. 25 Ma). L'exhumation finaledu facies de lherzolite à spinelle au facies à plagioclase et l'emplacement final dans la croûte, mieuxenregistrés dans Ronda, se sont produits par inversion et plissement de la section lithosphériquefortement amincie dans un contexte arrière-arc, probablement lors du retrait vers le sud de lalithosphère subduite et la collision de l'arc avec les paléo-marges maghrébines au Miocène inférieur(21-23 Ma). / The mantle deformation processes that control the thinning and break-up of continentallithosphere remain poorly understood. Our knowledge is restricted to either lithospheric scalethermo-mechanical models —that use experimentally derived flow laws—, geophysicalimaging and/or rare xenoliths from active continental rifts, such as the East African Rift System.The originality of this work relies on the study of the two largest outcrops of diamond faciessubcontinental lithospheric mantle in the world: the Beni Bousera and Ronda peridotite massifsin N Morocco and S Spain, respectively. The structures and petrologic and metamorphic zoningpreserved in these massifs —implying a polybaric and polythermal evolution— provide aunique opportunity to investigate the thermo-mechanical evolution of thick subcontinentallithospheric mantle in extensional settings.In this thesis we studied the deformation mechanisms in both peridotites andpyroxenites to constrain the modes of exhumation of subcontinental lithospheric mantle fromgarnet-, to spinel-, and finally, to plagioclase lherzolite facies conditions. We combined fieldmapping of tectono-metamorphic domains and structural mapping of ductile structures,microstructural analysis, crystal preferred orientations (CPO) measurements and conventionalthermobarometric calculations and thermodynamic modeling (Perple_X) to unravel the pressureand temperature conditions of deformation. We showed that exhumation from garnet- to spinellherzolite facies conditions was accommodated by fast shearing —in thermal disequilibrium—along a lithospheric scale transtensional shear zone. In this context, the petrological zoning andthe large temperature gradient (ca. 100ºC/km) preserved in the Beni Bousera massif representthe mechanical juxtaposition of progressively deeper and hotter lithospheric levels at depths ofca. 60 km in the latest Oligocene (ca. 25 Ma). Final exhumation from spinel- to plagioclasefacies lherzolite and emplacement into the crust is best recorded in the Ronda massif where itoccurred by inversion and lithospheric scale folding of the highly attenuated continentallithosphere in a back-arc region, probably in relation with southward slab rollback andsubsequent collision with the palaeo-Maghrebien passive margin in the early Miocene (21-23Ma).

Les recherches récentes sur le pluralisme socioéconomique et développemental dans le monde réhabilitent les intuitions de Polanyi : la révision fondamentale du sophisme économiste et l’encastrement de l’économique. Dans cette optique, la présente thèse a pour objet de penser l’articulation de trois phénomènes : le tiers secteur, le développement et la participation, à partir de l’observation des pratiques des acteurs du mouvement de solidarité associative à Beni Lubero, en RD Congo. Son approche pluridisciplinaire effectue, par une analyse beaucoup plus qualitative que quantitative, des allers et retours entre théories et faits empiriques in situ. Les deux premières parties tentent d’y identifier l’existence d’une gamme d’institutions susceptibles de compter parmi le tiers secteur compris, à l’interstice des secteurs public et privé et au creux d’autres concepts de l’économie plurielle, comme la stratégie d’auto-organisation collective, pour entreprendre ensemble et autrement ; en fonction d’un centre d’intérêts commun. La troisième partie, repensant le changement du paradigme du développement, assume celui-ci comme participatif par essence et, partant, stigmatise la pesanteur des interférences sur la conquête du concept ; et surtout en RD Congo. Elle vérifie combien, au sein de la société civile locale, le tiers-secteur de Beni Lubero est l'un des véritables leviers du processus d’auto-développement, grâce à sa multi-combativité participative. La dernière partie précise le contenu de la participation : son caractère trifacial (réfléchir, décider et agir), la nature triadique de son acte (s’associer, contribuer et bénéficier), les modes, techniques et méthodes de sa promotion ; ainsi que la transversalité de sa notion en sciences sociales et humaines. Puis, au filtre du design participatif d’Archon Fung, elle corrobore l’effectivité de la participation au sein du tiers secteur étudié. A moins de décrocher sa vigilance sur le balancier entre excellence et obstacle, la participation y paraît un tremplin à la plus-value incontestable ; notamment, en termes de membership, de leadership, d’entrepreneurship, de relationship et partnership, d’empowerment, d’ownership... / The recent research on the socioeconomic and developmental pluralism worldwide rehabilitate the insights of Polany i: fundamental review of sophistry economist (economist fallacy) and promoting the embedding of the economy. This thesis is in their view. Its purpose is to consider the linkages between three phenomena: the third sector, development and participation. To assess their articulation, it’s based on the observation of practices of the actors of various associations and solidarity movement in Beni Lubero, DR Congo. Its approach is multidisciplinary and its analysis is more qualitative than quantitative. It makes back and forth between theories and empirical facts in situ. The first two parts attempt to verify the existence of a range of institutions likely to be among third sector. The latter is then designed to the interstices of private and public socio- economic sectors; and in the hollow of the other concepts of the plural economy, such as collective self-organization strategy to undertake all together and otherwise; according to common interests. The third part rethinks the change in the development paradigm. It assumes that it’s essentially participatory. Therefore, it stigmatizes gravity of interference against the conquest of this concept, especially in DR Congo. Then, it checks how the Beni Lubero third sector, as part of the local civil society, is emerging as one of the real levers of self-development process, through its participatory multi-fighting. The final part specifies the content of participation: its triple facet (think, decide and act) and the triadic nature of its act (associate or join, contribute and benefit); methods, techniques and methods for its promotion; and the transversality of its concept through social sciences. Then, checking its practices through the participatory design of Archon Fung confirms the effectiveness of the participation in the Beni Lubero third sector. Unless failing in vigilance on the balance between excellence and obstacle, participation there seems a springboard whit a gain undeniable ; in particular, in development of membership, leadership, entrepreneurship, relationship, partnership, empowerment, ownership...

Le massif des Béni Snassen situé au Nord-Est du Maroc, se présente en un vaste dôme anticlinal essentiellement composé de terrains calcaires mésozoïques reposant sur un socle granito-schisteux paléozoïque. Par sa nature lithologique et par sa karstification ce massif contient des ressources hydrogéologiques d'une grande importance d'un point de vue économique (alimentation en eau, irrigation…) dans une zone en plein développement touristique, agricole et urbain. Ce travail a permis de mesurer la vulnérabilité des ressources karstiques en eau du massif afin de mettre en place des mesures de protection et de préservation de la ressource et fournir aux acteurs du territoire des outils et un support d'aide à la gestion et l'exploitation durables de cette ressource en eau. Pour répondre à cette problématique il a été nécessaire de croiser grâce aux « Systèmes d'Information Géographique » des données environnementales, anthropiques et territoriales. Cette approche a permis de spatialiser, croiser, superposer et pondérer les différentes couches d'information selon deux entrées : (i) l'entrée environnementale a permis de combiner le contexte géologique, l'évolution géomorphologique, la structuration hydrogéologique et les données bio-pédologique et climatique ; (ii) l'entrée anthropique pose les usages actuels et permet de prendre en compte les modes de réponse (en termes d'aménagement, de protection…) pour préserver la qualité de la ressource en eau. Les activités anthropiques fragilisent le système par la dégradation et la surexploitation des ressources naturelles (défrichement, coupe de bois, incendies, activités agro-pastorales non adaptées, etc.), mais aussi favorisent sa protection par le renforcement du milieu (construction des terrasses agricoles, reboisement, restauration, etc.). / The Beni Snassen massif located in northeastern Morocco corresponds to a vast anticline dome mainly composed of Mesozoic limestones which overlie a Paleozoic basement constituted of granite and schists. By its lithology and karstification this massif contains water resources of a strong economical and societal importance (water supply, irrigation ...) in an area where tourism, agriculture and towns rapidly develop. During this study we measured the vulnerability of karstic water resources of the massif in order to adopt measures for the protection and conservation of this heritage and for provide local actors with tools to help them for the management and sustainable exploitation of this water resource. To address this question it was necessary to cross environmental, human and territorial data through "Geographic Information Systems". This approach allows us to spatialize, cross, overlap and weight the different information layers by two inputs: (i) the environmental input combines geological framework, geomorphological evolution, hydrogeological and bio-soil and climate data; (ii) the anthropogenic input takes into account the current uses and the modes of response (in terms of development, protection ...) to preserve the quality of water resources. Human activities weakens the environmental system by the degradation and overexploitation of natural resources as land clearing, logging, fires, unsuitable agro-pastoral activities, etc… They can also promote its protection by strengthening the natural environment (construction of agricultural terraces, reforestation, restoration, etc.).

The aim of this thesis was to study the effects of extremely low frequency (ELF) electromagnetic magnetic fields on potassium currents in neural cell lines ( Neuroblastoma SK-N-BE ), using the whole-cell Patch Clamp technique. Such technique is a sophisticated tool capable to investigate the electrophysiological activity at a single cell, and even at single channel level. The total potassium ion currents through the cell membrane was measured while exposing the cells to a combination of static (DC) and alternate (AC) magnetic fields according to the prediction of the so-called ‘ Ion Resonance Hypothesis ’. For this purpose we have designed and fabricated a magnetic field exposure system reaching a good compromise between magnetic field homogeneity and accessibility to the biological sample under the microscope. The magnetic field exposure system consists of three large orthogonal pairs of square coils surrounding the patch clamp set up and connected to the signal generation unit, able to generate different combinations of static and/or alternate magnetic fields. Such system was characterized in term of field distribution and uniformity through computation and direct field measurements. No statistically significant changes in the potassium ion currents through cell membrane were reveled when the cells were exposed to AC/DC magnetic field combination according to the afore mentioned ‘Ion Resonance Hypothesis’.