Bayesian space-time data fusion for real-time forecasting and map uncertainty

Environmental computer models are deterministic models devoted to predict several environmental phenomena such as air pollution or meteorological events. Numerical model output is given in terms of averages over grid cells, usually at high spatial and temporal resolution. However, these outputs are often biased with unknown calibration and not equipped with any information about the associated uncertainty. Conversely, data collected at monitoring stations is more accurate since they essentially provide the true levels. Due the leading role played by numerical models, it now important to compare model output with observations. Statistical methods developed to combine numerical model output and station data are usually referred to as data fusion. In this work, we first combine ozone monitoring data with ozone predictions from the Eta-CMAQ air quality model in order to forecast real-time current 8-hour average ozone level defined as the average of the previous four hours, current hour, and predictions for the next three hours. We propose a Bayesian downscaler model based on first differences with a flexible coefficient structure and an efficient computational strategy to fit model parameters. Model validation for the eastern United States shows consequential improvement of our fully inferential approach compared with the current real-time forecasting system. Furthermore, we consider the introduction of temperature data from a weather forecast model into the downscaler, showing improved real-time ozone predictions. Finally, we introduce a hierarchical model to obtain spatially varying uncertainty associated with numerical model output. We show how we can learn about such uncertainty through suitable stochastic data fusion modeling using some external validation data. We illustrate our Bayesian model by providing the uncertainty map associated with a temperature output over the northeastern United States.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

The spatial representation of time

Numerosi studi mostrano che gli intervalli temporali sono rappresentati attraverso un codice spaziale che si estende da sinistra verso destra, dove gli intervalli brevi sono rappresentati a sinistra rispetto a quelli lunghi. Inoltre tale disposizione spaziale del tempo può essere influenzata dalla manipolazione dell’attenzione-spaziale. La presente tesi si inserisce nel dibattito attuale sulla relazione tra rappresentazione spaziale del tempo e attenzione-spaziale attraverso l’uso di una tecnica che modula l’attenzione-spaziale, ovvero, l’Adattamento Prismatico (AP). La prima parte è dedicata ai meccanismi sottostanti tale relazione. Abbiamo mostrato che spostando l’attenzione-spaziale con AP, verso un lato dello spazio, si ottiene una distorsione della rappresentazione di intervalli temporali, in accordo con il lato dello spostamento attenzionale. Questo avviene sia con stimoli visivi, sia con stimoli uditivi, nonostante la modalità uditiva non sia direttamente coinvolta nella procedura visuo-motoria di AP. Questo risultato ci ha suggerito che il codice spaziale utilizzato per rappresentare il tempo, è un meccanismo centrale che viene influenzato ad alti livelli della cognizione spaziale. La tesi prosegue con l’indagine delle aree corticali che mediano l’interazione spazio-tempo, attraverso metodi neuropsicologici, neurofisiologici e di neuroimmagine. In particolare abbiamo evidenziato che, le aree localizzate nell’emisfero destro, sono cruciali per l’elaborazione del tempo, mentre le aree localizzate nell’emisfero sinistro sono cruciali ai fini della procedura di AP e affinché AP abbia effetto sugli intervalli temporali. Infine, la tesi, è dedicata allo studio dei disturbi della rappresentazione spaziale del tempo. I risultati ci indicano che un deficit di attenzione-spaziale, dopo danno emisferico destro, provoca un deficit di rappresentazione spaziale del tempo, che si riflette negativamente sulla vita quotidiana dei pazienti. Particolarmente interessanti sono i risultati ottenuti mediante AP. Un trattamento con AP, efficace nel ridurre il deficit di attenzione-spaziale, riduce anche il deficit di rappresentazione spaziale del tempo, migliorando la qualità di vita dei pazienti.

Modelizzazione spazio-temporale delle dinamiche di uso del suolo ed analisi comparativa di differenti approcci predittivi. Uso integrato di SIG e telerilevamento nello studio dei processi di deforestazione nella regione La Joyanca in Peten, Guatemala

L’uso frequente dei modelli predittivi per l’analisi di sistemi complessi, naturali o artificiali, sta cambiando il tradizionale approccio alle problematiche ambientali e di rischio. Il continuo miglioramento delle capacità di elaborazione dei computer facilita l’utilizzo e la risoluzione di metodi numerici basati su una discretizzazione spazio-temporale che permette una modellizzazione predittiva di sistemi reali complessi, riproducendo l’evoluzione dei loro patterns spaziali ed calcolando il grado di precisione della simulazione. In questa tesi presentiamo una applicazione di differenti metodi predittivi (Geomatico, Reti Neurali, Land Cover Modeler e Dinamica EGO) in un’area test del Petén, Guatemala. Durante gli ultimi decenni questa regione, inclusa nella Riserva di Biosfera Maya, ha conosciuto una rapida crescita demografica ed un’incontrollata pressione sulle sue risorse naturali. L’area test puó essere suddivisa in sotto-regioni caratterizzate da differenti dinamiche di uso del suolo. Comprendere e quantificare queste differenze permette una migliore approssimazione del sistema reale; é inoltre necessario integrare tutti i parametri fisici e socio-economici, per una rappresentazione più completa della complessità dell’impatto antropico. Data l’assenza di informazioni dettagliate sull’area di studio, quasi tutti i dati sono stati ricavati dall’elaborazione di 11 immagini ETM+, TM e SPOT; abbiamo poi realizzato un’analisi multitemporale dei cambi uso del suolo passati e costruito l’input per alimentare i modelli predittivi. I dati del 1998 e 2000 sono stati usati per la fase di calibrazione per simulare i cambiamenti nella copertura terrestre del 2003, scelta come data di riferimento per la validazione dei risultati. Quest’ultima permette di evidenziare le qualità ed i limiti per ogni modello nelle differenti sub-regioni.

Numerical simulations of magma chamber dynamics at Campi Flegrei, and associated seismicity, deformation and gravity changes

Understanding the complex relationships between quantities measured by volcanic monitoring network and shallow magma processes is a crucial headway for the comprehension of volcanic processes and a more realistic evaluation of the associated hazard. This question is very relevant at Campi Flegrei, a volcanic quiescent caldera immediately north-west of Napoli (Italy). The system activity shows a high fumarole release and periodic ground slow movement (bradyseism) with high seismicity. This activity, with the high people density and the presence of military and industrial buildings, makes Campi Flegrei one of the areas with higher volcanic hazard in the world. In such a context my thesis has been focused on magma dynamics due to the refilling of shallow magma chambers, and on the geophysical signals detectable by seismic, deformative and gravimetric monitoring networks that are associated with this phenomenologies. Indeed, the refilling of magma chambers is a process frequently occurring just before a volcanic eruption; therefore, the faculty of identifying this dynamics by means of recorded signal analysis is important to evaluate the short term volcanic hazard. The space-time evolution of dynamics due to injection of new magma in the magma chamber has been studied performing numerical simulations with, and implementing additional features in, the code GALES (Longo et al., 2006), recently developed and still on the upgrade at the Istituto Nazionale di Geofisica e Vulcanologia in Pisa (Italy). GALES is a finite element code based on a physico-mathematical two dimensional, transient model able to treat fluids as multiphase homogeneous mixtures, compressible to incompressible. The fundamental equations of mass, momentum and energy balance are discretised both in time and space using the Galerkin Least-Squares and discontinuity-capturing stabilisation technique. The physical properties of the mixture are computed as a function of local conditions of magma composition, pressure and temperature.The model features enable to study a broad range of phenomenologies characterizing pre and sin-eruptive magma dynamics in a wide domain from the volcanic crater to deep magma feeding zones. The study of displacement field associated with the simulated fluid dynamics has been carried out with a numerical code developed by the Geophysical group at the University College Dublin (O’Brien and Bean, 2004b), with whom we started a very profitable collaboration. In this code, the seismic wave propagation in heterogeneous media with free surface (e.g. the Earth’s surface) is simulated using a discrete elastic lattice where particle interactions are controlled by the Hooke’s law. This method allows to consider medium heterogeneities and complex topography. The initial and boundary conditions for the simulations have been defined within a coordinate project (INGV-DPC 2004-06 V3_2 “Research on active volcanoes, precursors, scenarios, hazard and risk - Campi Flegrei”), to which this thesis contributes, and many researchers experienced on Campi Flegrei in volcanological, seismic, petrological, geochemical fields, etc. collaborate. Numerical simulations of magma and rock dynamis have been coupled as described in the thesis. The first part of the thesis consists of a parametric study aimed at understanding the eect of the presence in magma of carbon dioxide in magma in the convection dynamics. Indeed, the presence of this volatile was relevant in many Campi Flegrei eruptions, including some eruptions commonly considered as reference for a future activity of this volcano. A set of simulations considering an elliptical magma chamber, compositionally uniform, refilled from below by a magma with volatile content equal or dierent from that of the resident magma has been performed. To do this, a multicomponent non-ideal magma saturation model (Papale et al., 2006) that considers the simultaneous presence of CO2 and H2O, has been implemented in GALES. Results show that the presence of CO2 in the incoming magma increases its buoyancy force promoting convection ad mixing. The simulated dynamics produce pressure transients with frequency and amplitude in the sensitivity range of modern geophysical monitoring networks such as the one installed at Campi Flegrei . In the second part, simulations more related with the Campi Flegrei volcanic system have been performed. The simulated system has been defined on the basis of conditions consistent with the bulk of knowledge of Campi Flegrei and in particular of the Agnano-Monte Spina eruption (4100 B.P.), commonly considered as reference for a future high intensity eruption in this area. The magmatic system has been modelled as a long dyke refilling a small shallow magma chamber; magmas with trachytic and phonolitic composition and variable volatile content of H2O and CO2 have been considered. The simulations have been carried out changing the condition of magma injection, the system configuration (magma chamber geometry, dyke size) and the resident and refilling magma composition and volatile content, in order to study the influence of these factors on the simulated dynamics. Simulation results allow to follow each step of the gas-rich magma ascent in the denser magma, highlighting the details of magma convection and mixing. In particular, the presence of more CO2 in the deep magma results in more ecient and faster dynamics. Through this simulations the variation of the gravimetric field has been determined. Afterward, the space-time distribution of stress resulting from numerical simulations have been used as boundary conditions for the simulations of the displacement field imposed by the magmatic dynamics on rocks. The properties of the simulated domain (rock density, P and S wave velocities) have been based on data from literature on active and passive tomographic experiments, obtained through a collaboration with A. Zollo at the Dept. of Physics of the Federici II Univeristy in Napoli. The elasto-dynamics simulations allow to determine the variations of the space-time distribution of deformation and the seismic signal associated with the studied magmatic dynamics. In particular, results show that these dynamics induce deformations similar to those measured at Campi Flegrei and seismic signals with energies concentrated on the typical frequency bands observed in volcanic areas. The present work shows that an approach based on the solution of equations describing the physics of processes within a magmatic fluid and the surrounding rock system is able to recognise and describe the relationships between geophysical signals detectable on the surface and deep magma dynamics. Therefore, the results suggest that the combined study of geophysical data and informations from numerical simulations can allow in a near future a more ecient evaluation of the short term volcanic hazard.

Characterization of geothermal reservoirs’ parameters by inverse problem resolution and geostatistical simulations

BTES (borehole thermal energy storage)systems exchange thermal energy by conduction with the surrounding ground through borehole materials. The spatial variability of the geological properties and the space-time variability of hydrogeological conditions affect the real power rate of heat exchangers and, consequently, the amount of energy extracted from / injected into the ground. For this reason, it is not an easy task to identify the underground thermal properties to use when designing. At the current state of technology, Thermal Response Test (TRT) is the in situ test for the characterization of ground thermal properties with the higher degree of accuracy, but it doesn’t fully solve the problem of characterizing the thermal properties of a shallow geothermal reservoir, simply because it characterizes only the neighborhood of the heat exchanger at hand and only for the test duration. Different analytical and numerical models exist for the characterization of shallow geothermal reservoir, but they are still inadequate and not exhaustive: more sophisticated models must be taken into account and a geostatistical approach is needed to tackle natural variability and estimates uncertainty. The approach adopted for reservoir characterization is the “inverse problem”, typical of oil&gas field analysis. Similarly, we create different realizations of thermal properties by direct sequential simulation and we find the best one fitting real production data (fluid temperature along time). The software used to develop heat production simulation is FEFLOW 5.4 (Finite Element subsurface FLOW system). A geostatistical reservoir model has been set up based on literature thermal properties data and spatial variability hypotheses, and a real TRT has been tested. Then we analyzed and used as well two other codes (SA-Geotherm and FV-Geotherm) which are two implementation of the same numerical model of FEFLOW (Al-Khoury model).

Luis Cernuda: la realizzazione del desiderio

Le traduzioni di Luis Cernuda, poeta spagnolo della Generazione del '27, da testi poetici di autori francesi, tedeschi ed inglesi, la cui scelta è dettata da ragioni di coerenza artistica, non hanno valore secondario rispetto alla produzione poetica autoriale. Nel presente studio si delinea l'uniformità del percorso creativo di Luis Cernuda nel ruolo duplice ed apparentemente contraddittorio di poeta-traduttore, attraverso un tracciato spazio-temporale, al contempo realistico e metaforico, che si svolge lungo gran parte della vita del misconosciuto poeta sivigliano. Ad una preliminare presentazione analitica del concetto di traduzione, della funzione che la stessa riveste nel genere letterario specifico della poesia e nell'attività creativa di Cernuda, segue l'analisi comparativa delle traduzioni cernudiane con le rispettive fonti straniere. L'argomento si svolge in tre capitoli successivi, organizzati rispettando lo svolgimento cronologico del percorso traduttorio cernudiano, svolto in parallelo alla produzione poetica personale. Il secondo capitolo verte sulla traduzione da testi poetici in francese. Il terzo capitolo, sul periodo immediatamente successivo agli anni della sperimentazione francese, analizza lo studio della poesia tedesca e della sperimentazione in traduzione. Tale incontro si propone anche come momento di scissione definitiva dalla lirica romanza, piuttosto esornativa, e di accostamento alla più essenziale lirica germanica. Il quarto capitolo raccoglie le versioni poetiche da autori inglesi, che si contraddistinguono per la grande somiglianza alla poesia di Cernuda nelle scelte contenutistico-formali. Le conclusioni vertono sulla coesione perseguita nel tradurre, per cui contenuto e forma acquisiscono pari importanza nella “ricreazione poetica” realizzata da Cernuda.