Continuous geochemical monitoring by mass-spectometer in the Campi Flegrei geothermal area. An application at Pisciarelli-Solfatara (diffuse and fumarolic gases) and at the mud gases during drilling of the CFDDP pilot hole

During this work has been developed an innovative methodology for continuous and in situ gas monitoring (24/24 h) of fumarolic and soil diffusive emissions applied to the geothermal and volcanic area of Pisciarelli near Agnano inside the Campi Flegrei caldera (CFc). In literature there are only scattered and in discrete data of the geochemical gas composition of fumarole at Campi Flegrei; it is only since the early ’80 that exist a systematic record of fumaroles with discrete sampling at Solfatara (Bocca Grande and Bocca Nuova fumaroles) and since 1999, even at the degassing areas of Pisciarelli. This type of sampling has resulted in a time series of geochemical analysis with discontinuous periods of time set (in average 2-3 measurements per month) completely inadequate for the purposes of Civil Defence in such high volcanic risk and densely populated areas. For this purpose, and to remedy this lack of data, during this study was introduced a new methodology of continuous and in situ sampling able to continuously detect data related and from its soil diffusive degassing. Due to its high sampling density (about one measurement per minute therefore producing 1440 data daily) and numerous species detected (CO2, Ar, 36Ar, CH4, He, H2S, N2, O2) allowing a good statistic record and the reconstruction of the gas composition evolution of the investigated area. This methodology is based on continuous sampling of fumaroles gases and soil degassing using an extraction line, which after undergoing a series of condensation processes of the water vapour content - better described hereinafter - is analyzed through using a quadrupole mass spectrometer

Statistical Physics and Modeling of Human Mobility

In this thesis, we extend some ideas of statistical physics to describe the properties of human mobility. By using a database containing GPS measures of individual paths (position, velocity and covered space at a spatial scale of 2 Km or a time scale of 30 sec), which includes the 2% of the private vehicles in Italy, we succeed in determining some statistical empirical laws pointing out "universal" characteristics of human mobility. Developing simple stochastic models suggesting possible explanations of the empirical observations, we are able to indicate what are the key quantities and cognitive features that are ruling individuals' mobility. To understand the features of individual dynamics, we have studied different aspects of urban mobility from a physical point of view. We discuss the implications of the Benford's law emerging from the distribution of times elapsed between successive trips. We observe how the daily travel-time budget is related with many aspects of the urban environment, and describe how the daily mobility budget is then spent. We link the scaling properties of individual mobility networks to the inhomogeneous average durations of the activities that are performed, and those of the networks describing people's common use of space with the fractional dimension of the urban territory. We study entropy measures of individual mobility patterns, showing that they carry almost the same information of the related mobility networks, but are also influenced by a hierarchy among the activities performed. We discover that Wardrop's principles are violated as drivers have only incomplete information on traffic state and therefore rely on knowledge on the average travel-times. We propose an assimilation model to solve the intrinsic scattering of GPS data on the street network, permitting the real-time reconstruction of traffic state at a urban scale.

Investigation of the lithium ion mobility in cyclic model compounds and their ion conducting properties

Efficient energy storage and conversion is playing a key role in overcoming the present and future challenges in energy supply. Batteries provide portable, electrochemical storage of green energy sources and potentially allow for a reduction of the dependence on fossil fuels, which is of great importance with respect to the issue of global warming. In view of both, energy density and energy drain, rechargeable lithium ion batteries outperform other present accumulator systems. However, despite great efforts over the last decades, the ideal electrolyte in terms of key characteristics such as capacity, cycle life, and most important reliable safety, has not yet been identified. rnrnSteps ahead in lithium ion battery technology require a fundamental understanding of lithium ion transport, salt association, and ion solvation within the electrolyte. Indeed, well-defined model compounds allow for systematic studies of molecular ion transport. Thus, in the present work, based on the concept of ‘immobilizing’ ion solvents, three main series with a cyclotriphosphazene (CTP), hexaphenylbenzene (HBP), and tetramethylcyclotetrasiloxane (TMS) scaffold were prepared. Lithium ion solvents, among others ethylene carbonate (EC), which has proven to fulfill together with pro-pylene carbonate safety and market concerns in commercial lithium ion batteries, were attached to the different cores via alkyl spacers of variable length.rnrnAll model compounds were fully characterized, pure and thermally stable up to at least 235 °C, covering the requested broad range of glass transition temperatures from -78.1 °C up to +6.2 °C. While the CTP models tend to rearrange at elevated temperatures over time, which questions the general stability of alkoxide related (poly)phosphazenes, both, the HPB and CTP based models show no evidence of core stacking. In particular the CTP derivatives represent good solvents for various lithium salts, exhibiting no significant differences in the ionic conductivity σ_dc and thus indicating comparable salt dissociation and rather independent motion of cations and ions.rnrnIn general, temperature-dependent bulk ionic conductivities investigated via impedance spectroscopy follow a William-Landel-Ferry (WLF) type behavior. Modifications of the alkyl spacer length were shown to influence ionic conductivities only in combination to changes in glass transition temperatures. Though the glass transition temperatures of the blends are low, their conductivities are only in the range of typical polymer electrolytes. The highest σ_dc obtained at ambient temperatures was 6.0 x 10-6 S•cm-1, strongly suggesting a rather tight coordination of the lithium ions to the solvating 2-oxo-1,3-dioxolane moieties, supported by the increased σ_dc values for the oligo(ethylene oxide) based analogues.rnrnFurther insights into the mechanism of lithium ion dynamics were derived from 7Li and 13C Solid- State NMR investigations. While localized ion motion was probed by i.e. 7Li spin-lattice relaxation measurements with apparent activation energies E_a of 20 to 40 kJ/mol, long-range macroscopic transport was monitored by Pulsed-Field Gradient (PFG) NMR, providing an E_a of 61 kJ/mol. The latter is in good agreement with the values determined from bulk conductivity data, indicating the major contribution of ion transport was only detected by PFG NMR. However, the μm-diffusion is rather slow, emphasizing the strong lithium coordination to the carbonyl oxygens, which hampers sufficient ion conductivities and suggests exploring ‘softer’ solvating moieties in future electrolytes.rn

Black hole evaporation and stress tensor correlations

General Relativity is one of the greatest scientific achievementes of the 20th century along with quantum theory. These two theories are extremely beautiful and they are well verified by experiments, but they are apparently incompatible. Hints towards understanding these problems can be derived studying Black Holes, some the most puzzling solutions of General Relativity. The main topic of this Master Thesis is the study of Black Holes, in particular the Physics of Hawking Radiation. After a short review of General Relativity, I study in detail the Schwarzschild solution with particular emphasis on the coordinates systems used and the mathematical proof of the classical laws of Black Hole "Thermodynamics". Then I introduce the theory of Quantum Fields in Curved Spacetime, from Bogolubov transformations to the Schwinger-De Witt expansion, useful for the renormalization of the stress energy tensor. After that I introduce a 2D model of gravitational collapse to study the Hawking radiation phenomenon. Particular emphasis is given to the analysis of the quantum states, from correlations to the physical implication of this quantum effect (e.g. Information Paradox, Black Hole Thermodynamics). Then I introduce the renormalized stress energy tensor. Using the Schwinger-De Witt expansion I renormalize this object and I compute it analytically in the various quantum states of interest. Moreover, I study the correlations between these objects. They are interesting because they are linked to the Hawking radiation experimental search in acoustic Black Hole models. In particular I find that there is a characteristic peak in correlations between points inside and outside the Black Hole region, which correpsonds to entangled excitations inside and outside the Black Hole. These peaks hopefully will be measurable soon in supersonic BEC.

Classical and quantum aspects of black hole dynamics

Il contenuto fisico della Relatività Generale è espresso dal Principio di Equivalenza, che sancisce l'equivalenza di geometria e gravitazione. La teoria predice l'esistenza dei buchi neri, i più semplici oggetti macroscopici esistenti in natura: essi sono infatti descritti da pochi parametri, le cui variazioni obbediscono a leggi analoghe a quelle della termodinamica. La termodinamica dei buchi neri è posta su basi solide dalla meccanica quantistica, mediante il fenomeno noto come radiazione di Hawking. Questi risultati gettano una luce su una possibile teoria quantistica della gravitazione, ma ad oggi una simile teoria è ancora lontana. In questa tesi ci proponiamo di studiare i buchi neri nei loro aspetti sia classici che quantistici. I primi due capitoli sono dedicati all'esposizione dei principali risultati raggiunti in ambito teorico: in particolare ci soffermeremo sui singularity theorems, le leggi della meccanica dei buchi neri e la radiazione di Hawking. Il terzo capitolo, che estende la discussione sulle singolarità, espone la teoria dei buchi neri non singolari, pensati come un modello effettivo di rimozione delle singolarità. Infine il quarto capitolo esplora le ulteriori conseguenze della meccanica quantistica sulla dinamica dei buchi neri, mediante l'uso della nozione di entropia di entanglement.

Black Hole and Galaxy Growth over Cosmic Time: the Chandra COSMOS Legacy Survey

The study of supermassive black hole (SMBH) accretion during their phase of activity (hence becoming active galactic nuclei, AGN), and its relation to the host-galaxy growth, requires large datasets of AGN, including a significant fraction of obscured sources. X-ray data are strategic in AGN selection, because at X-ray energies the contamination from non-active galaxies is far less significant than in optical/infrared surveys, and the selection of obscured AGN, including also a fraction of heavily obscured AGN, is much more effective. In this thesis, I present the results of the Chandra COSMOS Legacy survey, a 4.6 Ms X-ray survey covering the equatorial COSMOS area. The COSMOS Legacy depth (flux limit f=2x10^(-16) erg/s/cm^(-2) in the 0.5-2 keV band) is significantly better than that of other X-ray surveys on similar area, and represents the path for surveys with future facilities, like Athena and X-ray Surveyor. The final Chandra COSMOS Legacy catalog contains 4016 point-like sources, 97% of which with redshift. 65% of the sources are optically obscured and potentially caught in the phase of main BH growth. We used the sample of 174 Chandra COSMOS Legacy at z>3 to place constraints on the BH formation scenario. We found a significant disagreement between our space density and the predictions of a physical model of AGN activation through major-merger. This suggests that in our luminosity range the BH triggering through secular accretion is likely preferred to a major-merger triggering scenario. Thanks to its large statistics, the Chandra COSMOS Legacy dataset, combined with the other multiwavelength COSMOS catalogs, will be used to answer questions related to a large number of astrophysical topics, with particular focus on the SMBH accretion in different luminosity and redshift regimes.

High mobility rates during the period of the "Celtic migrations"? - 87 Sr, 86 Sr and delta 18 O evidence from Early La Tène Europe

Although the period of the historic “Celtic migrations” is archaeologically extensively studied, the long-lasting question whether mass migration or increased individual mobility caused the expansion of the La Tène culture throughout continental Europe persist. Strontium (Sr) and in part oxygen (O) isotope analysis of human remains from the early La Tène cemeteries of Nebringen (Germany), Münsingen-Rain (Switzerland), Monte Bibele (Italy) and the Czech cemeteries of Radovesice I, Radovesice II and Kutná Hora was, therefore, carried out to investigate the importance of residential changes during this time period. These isotope analyses showed that most analysed individuals either came from the area they were buried in or from the surrounding area of the cemetery. An exception was formed by the Czech cemeteries, where almost a quarter of the studied individuals appeared non-local. Together with Nebringen, these cemeteries also had the most varied Sr isotope ratios, which suggest highly mobile communities in which individuals regularly changed their residency. The isotopic ratios of the cemeteries of Münsingen-Rain and Monte Bibele appeared far less varied. In part, these differences might be explained by the community structures of these cemeteries. Morphological kinship analysis in Münsingen-Rain demonstrated biological relatedness among most of the analysed individuals. These related individuals also shared similar isotope signatures, which suggest an origin from the surrounding Aar Valley. In the vicinity of the cemetery of Monte Bibele, an associated settlement site was discovered. The deceased presumably not only shared this settlement, but also cultivated the same land plots. Dispersed settlement structures were suggested for Nebringen, Radovesice and Kutná Hora, as these agriculturally favourable landscapes were densely populated during prehistoric times. Connected to these community structures are the prevailing geological conditions in these areas. Both Münsingen-Rain and Monte Bibele are located in a region where homogeneous geological conditions prevail, whereas the landscapes of Nebringen, Radovesice and Kutná Hora are characterised by complex heterogeneous geological conditions. As the majority of individuals in Nebringen and the Czech cemeteries correspond to the expected isotope values for the studied areas, regularly changing land plots might have contributed to the observed variation. Although mass migration as depicted by the historical sources was not observed individual mobility of a small part of these studied communities certainly played a role. Males appeared, thereby, to have slightly more often a non-local birthplace or moved during childhood. Male mobility was, however, not always associated with burial as a warrior. Females, on the other hand, originated more often from the region. Patrilocal residential patterns, with the exception of the Czech cemeteries, were nevertheless not observed. Objects and ideas also seem to have been exchanged freely, as there are no indications that individuals with particular grave goods came from specific areas. It rather appears that the individuals buried with them were either local or had different places of origin. This can be explained by the fact that the exact origin of grave goods is difficult to establish and the occurrence of similar 87Sr/86Sr values in different areas. This study provided important new insights on the period of the “Celtic migrations” and the way of life of these prehistoric people.

Integration of a simulation platform for electrical mobility within the arrowhead interoperability framework

This dissertation document deals with the development of a project, over a span of more than two years, carried out within the scope of the Arrowhead Framework and which bears my personal contribution in several sections. The final part of the project took place during a visiting period at the university of Luleå. The Arrowhead Project is an European project, belonging to the ARTEMIS association, which aims to foster new technologies and unify the access to them into an unique framework. Such technologies include the Internet of Things phe- nomenon, Smart Houses, Electrical Mobility and renewable energy production. An application is considered compliant with such framework when it respects the Service Oriented Architecture paradigm and it is able to interact with a set of defined components called Arrowhead Core Services. My personal contribution to this project is given by the development of several user-friendly API, published in the project's main repository, and the integration of a legacy system within the Arrowhead Framework. The implementation of this legacy system was initiated by me in 2012 and, after many improvements carried out by several developers in UniBO, it has been again significantly modified this year in order to achieve compatibility. The system consists of a simulation of an urban scenario where a certain amount of electrical vehicles are traveling along their specified routes. The vehicles are con-suming their battery and, thus, need to recharge at the charging stations. The electrical vehicles need to use a reservation mechanism to be able to recharge and avoid waiting lines, due to the long recharge process. The integration with the above mentioned framework consists in the publication of the services that the system provides to the end users through the instantiation of several Arrowhead Service Producers, together with a demo Arrowhead- compliant client application able to consume such services.

Studio di celle solari innovative basate su "multiple electron-hole generation"

L’aumento dei consumi energetici e la sempre maggiore attenzione posta al tema ambientale fanno delle energie alternative una valida alternativa alle fonti , quali carbone e petrolio,che presentano una elevata generazione di gas serra . Tra le varie fonti alternative di energia un ruolo preponderante è stato assunto dal solare fotovoltaico, che dagli anni ’80 ad oggi ha conosciuto un rapido sviluppo sia in termini di ricerca che di utilizzo su larga scala. Negli ultimi anni tutti gli studi si stanno concentrando su un nuovo tipo di fotovoltaico, quello di terza generazione , il cui scopo è quello di ottenere dispositivi che possano garantire elevate efficienze in modo tale che la tecnologia fotovoltaica sia in grado di affermarsi definitivamente nel settore dell’energia. Il presente lavoro di tesi analizza il processo di conversione fotovoltaica ed il principio di funzionamento delle celle solari . I limiti termodinamici per l'efficienza di conversione di celle solari a singola giunzione sono stati discussi nella tesi. E' presentata nella tesi una rassegna delle principali strategie per il superamento dei limiti termodinamici per l'efficienza di una cella solare a singola giunzione . Sono stati analizzati : •il processo di rilassamento intrabanda dei nanocristalli ; •la generazione multipla di eccitoni (MEG) •il processo di Generazione di eccitoni multipli in nanocristalli di silicio colloidali (MEG in Si NCs). Tali risultati rivestono un particolare interesse per lo sviluppo di celle solari innovative , ad alta efficienza di conversione , utilizzando un materiale facilmente reperibile ed economico come appunto è il Silicio.

Smart Mobility: integrazione di crowdsourcing e opendata per percorsi multimodali e personalizzati.

Lo scopo che questa tesi ha è di inserirsi nell’ambito della Smart Mobility, in particolare nell'ambito dell’accessibilità urbana. Obiettivo primario è di offrire un software capace di adattarsi alle capacità dell’utente nel muoversi nell’ambiente urbano, in particolare riguardo alle barriere architettoniche che lo ostacolano. Quello che il programma deve fare è offrire percorsi per l’utente, personalizzati rispetto alle sue richieste. Affinché sia possibile tutto ciò, sono necessarie delle fondamenta, nella fattispecie una fonte di dati geografici e uno strumento che permetta di ricercare percorsi da essi e di essere modificato per includere le modifiche volute. La fonte di dati geografici scelta è stata OpenStreetMap, un progetto di crowdsourcing che punta a creare una mappa globale completamente accessibile fino al suo livello più basso e utilizzabile da chiunque, purché sia rispettata la sua licenza. Da questa scelta, derivano i software utilizzabili per calcolare i percorsi: la tesi ne esplorerà in particolare due GraphHopper e OpenTripPlanner, entrambi progetti open source. L’ultimo, ma non meno importante, scopo della tesi è effettivamente implementare un algoritmo di routing capace di considerare le preferenze degli utenti. Queste preferenze, infatti, non devono solo permettere di escludere percorsi con una barriera/architettonica cui l’utente non può accedere, ma anche di favorire percorsi con le facility che l’utente preferisce e di sfavorire quelli con facility che l’utente non preferisce.

Applicazioni della tecnica di misura incremental hole drilling per provini sottili

Allo scopo di valutare le tensioni residue di un pannello in alluminio sottile, è stata sviluppata la tecnica definita Incremental Hole Drilling. Poichè tale tecnica è applicata a componenti di spessori rilevanti, per ovviare alle problematiche di vibrazione del provino è stata applicata una controlastra di resina polimerizzata per aumentare la rigidezza flessionale. Le analisi effettuate hanno mostrato una influenza della resina non trascurabile sullo stato di tensione del materiale.

Determinazione delle tensioni residue in componenti metallici sottili mediante "incremental hole drilling"

La vita di un aeromobile è un elemento importante sia per quanto riguarda la sicurezza del payload, che da un punto di vista economico, a causa delle spese di manutenzione/rinnovamento della flotta che una compagnia aerea deve affrontare. Gli elementi costitutivi di un aeromobile sono soggetti a diverse tipologie di carichi, alcuni dei quali ciclici come la pressurizzazione/depressurizzazione della fusoliera; tali carichi, nel lungo periodo, possono provocare la nascita e la propagazione di eventuali cricche, le quali possono portare alla rottura del componente stesso causando gravi incidenti. Il legame tra tensioni residue e nascita/crescita delle cricche ha portato allo sviluppo di tecniche per contrastare questo fenomeno, come il processo del LSP. Per la misura delle tensioni residue esistono già normative di riferimento, le quali però non trattano componenti metallici di piccolo spessore mentre i pannelli di fusoliera rientrano in questa categoria. Scopo di questa tesi è quello di studiare una variante della tecnica HD adatta a valutare le tensioni residue in componenti metallici di piccolo spessore e confrontare i risultati con quelli ottenuti con la tecnica XRD. L’idea di partenza è l’implementazione di un supporto posteriore in resina che simuli la presenza di uno spessore maggiore.

Localization and mobility-edges in non-interacting fermionic models with disorder

Nel corso degli ultimi decenni la fisica sperimentale ha raggiunto notevoli traguardi nel campo della manipolazione di sistemi di atomi freddi, riaccendendo l'interesse della ricerca su sistemi a lungo studiati teoricamente, ma fino a poco tempo fa impossibili da realizzare sperimentalmente. Questa riaccesa attenzione ha permesso di sfruttare le moderne capacità di calcolo per studiare sistemi quantistici che ancora risultano di difficile realizzazione. In questo contesto si inserisce il rinnovato interesse per i sistemi quantistici monodimensionali caratterizzati dalla presenza di potenziale disordinato. Questi presentano proprietà di trasporto particolari e sotto particolari condizioni sono oggetto di una transizione di localizzazione. La maggior parte degli studi in questo campo rivolgono la loro attenzione a sistemi di particelle fermioniche interagenti. In questo lavoro di tesi analizziamo, invece, sistemi quantistici fermionici non interagenti, mettendo in luce quanto già noto e proponendo strumenti di analisi derivati dallo studio dei sistemi interagenti. In particolare, proponiamo un'analisi statistica dei livelli energetici e poniamo le basi per futuri studi a riguardo.

Crowdsensing and proximity services for impaired mobility

La tesi si occupa della creazione di una piattaforma virtuale, composta da un sito web e da una applicazione Android, a supporto di persone con handicap motori. La piattaforma e composta da una mappa interattiva che permette agli utenti di inserire nuovi locali o di commentarne esistenti, e di fare lo stesso per le barriere architettoniche. Per questi motivi il progetto e dettato da una continua comunicazione tra client e server, rendendo la piattaforma aggiornata e dinamica, anche alla vista degli utenti. La parte web viene implementata attraverso Spring MVC, utilizzando delle View .jsp ed AJAX per la comunicazione remota con il server. La parte mobile e stata implementata basandosi principalmente sulle classi di geolocalizzazione di Android, oltre alle librerie osmdroid ed osmbonuspack, fornendo compatitiblita con OSM. Questa fornisce anche un servizio di calcolo del percorso, cercando di evitare il numero maggiore di ostacoli. L'applicazione Android appoggia le proprie comunicazioni sulla libreria Robospice. La parte di persistenza e stata implementata adottando un approccio ad alto livello, grazie ad Hibernate e JPA.