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

The collapse of linear polyelectrolyte chains in a poor solvent: When does a collapsing polyelectrolyte collect its counter ions?

The collapse of linear polyelectrolyte chains in a poor solvent: When does a collapsing polyelectrolyte collect its counter ions? The collapse of polyions in a poor solvent is a complex system and is an active research subject in the theoretical polyelectrolyte community. The complexity is due to the subtle interplay between hydrophobic effects, electrostatic interactions, entropy elasticity, intrinsic excluded volume as well as specific counter-ion and co-ion properties. Long range Coulomb forces can obscure single molecule properties. The here presented approach is to use just a small amount of screening salt in combination with a very high sample dilution in order to screen intermolecular interaction whereas keeping intramolecular interaction as much as possible (polyelectrolyte concentration cp ≤ 12 mg/L, salt concentration; Cs = 10^-5 mol/L). This is so far not described in literature. During collapse, the polyion is subject to a drastic change in size along with strong reduction of free counterions in solution. Therefore light scattering was utilized to obtain the size of the polyion whereas a conductivity setup was developed to monitor the proceeding of counterion collection by the polyion. Partially quaternized PVP’s below and above the Manning limit were investigated and compared to the collapse of their uncharged precursor. The collapses were induced by an isorefractive solvent/non-solvent mixture consisting of 1-propanol and 2-pentanone, with nearly constant dielectric constant. The solvent quality for the uncharged polyion could be quantified which, for the first time, allowed the experimental investigation of the effect of electrostatic interaction prior and during polyion collapse. Given that the Manning parameter M for QPVP4.3 is as low as lB / c = 0.6 (lB the Bjerrum length and c the mean contour distance between two charges), no counterion binding should occur. However the Walden product reduces with first addition of non solvent and accelerates when the structural collapse sets in. Since the dielectric constant of the solvent remains virtually constant during the chain collapse, the counterion binding is entirely caused by the reduction in the polyion chain dimension. The collapse is shifted to lower wns with higher degrees of quaternization as the samples QPVP20 and QPVP35 show (M = 2.8 respectively 4.9). The combination of light scattering and conductivity measurement revealed for the first time that polyion chains already collect their counter ions well above the theta-dimension when the dimensions start to shrink. Due to only small amounts of screening salt, strong electrostatic interactions bias dynamic as well as static light scattering measurements. An extended Zimm formula was derived to account for this interaction and to obtain the real chain dimensions. The effective degree of dissociation g could be obtained semi quantitatively using this extrapolated static in combination with conductivity measurements. One can conclude the expansion factor a and the effective degree of ionization of the polyion to be mutually dependent. In the good solvent regime g of QPVP4.3, QPVP20 and QPVP35 exhibited a decreasing value in the order 1 > g4.3 > g20 > g35. The low values of g for QPVP20 and QPVP35 are assumed to be responsible for the prior collapse of the higher quaternized samples. Collapse theory predicts dipole-dipole attraction to increase accordingly and even predicts a collapse in the good solvent regime. This could be exactly observed for the QPVP35 sample. The experimental results were compared to a newly developed theory of uniform spherical collapse induced by concomitant counterion binding developed by M. Muthukumar and A. Kundagrami. The theory agrees qualitatively with the location of the phase boundary as well as the trend of an increasing expansion with an increase of the degree of quaternization. However experimental determined g for the samples QPVP4.3, QPVP20 and QPVP35 decreases linearly with the degree of quaternization whereas this theory predicts an almost constant value.

Lesion detection and classification in breast cancer: evaluation of approaches based on morphological features, tracer kinetic modelling and semi-quantitative parameters in MR functional imaging (DCE-MRI)

The diagnosis, grading and classification of tumours has benefited considerably from the development of DCE-MRI which is now essential to the adequate clinical management of many tumour types due to its capability in detecting active angiogenesis. Several strategies have been proposed for DCE-MRI evaluation. Visual inspection of contrast agent concentration curves vs time is a very simple yet operator dependent procedure, therefore more objective approaches have been developed in order to facilitate comparison between studies. In so called model free approaches, descriptive or heuristic information extracted from time series raw data have been used for tissue classification. The main issue concerning these schemes is that they have not a direct interpretation in terms of physiological properties of the tissues. On the other hand, model based investigations typically involve compartmental tracer kinetic modelling and pixel-by-pixel estimation of kinetic parameters via non-linear regression applied on region of interests opportunely selected by the physician. This approach has the advantage to provide parameters directly related to the pathophysiological properties of the tissue such as vessel permeability, local regional blood flow, extraction fraction, concentration gradient between plasma and extravascular-extracellular space. Anyway, nonlinear modelling is computational demanding and the accuracy of the estimates can be affected by the signal-to-noise ratio and by the initial solutions. The principal aim of this thesis is investigate the use of semi-quantitative and quantitative parameters for segmentation and classification of breast lesion. The objectives can be subdivided as follow: describe the principal techniques to evaluate time intensity curve in DCE-MRI with focus on kinetic model proposed in literature; to evaluate the influence in parametrization choice for a classic bi-compartmental kinetic models; to evaluate the performance of a method for simultaneous tracer kinetic modelling and pixel classification; to evaluate performance of machine learning techniques training for segmentation and classification of breast lesion.

Solutions to common issues in widefield microscopy: vignetting, mosaicing and depth of focus

In this thesis we have developed solutions to common issues regarding widefield microscopes, facing the problem of the intensity inhomogeneity of an image and dealing with two strong limitations: the impossibility of acquiring either high detailed images representative of whole samples or deep 3D objects. First, we cope with the problem of the non-uniform distribution of the light signal inside a single image, named vignetting. In particular we proposed, for both light and fluorescent microscopy, non-parametric multi-image based methods, where the vignetting function is estimated directly from the sample without requiring any prior information. After getting flat-field corrected images, we studied how to fix the problem related to the limitation of the field of view of the camera, so to be able to acquire large areas at high magnification. To this purpose, we developed mosaicing techniques capable to work on-line. Starting from a set of overlapping images manually acquired, we validated a fast registration approach to accurately stitch together the images. Finally, we worked to virtually extend the field of view of the camera in the third dimension, with the purpose of reconstructing a single image completely in focus, stemming from objects having a relevant depth or being displaced in different focus planes. After studying the existing approaches for extending the depth of focus of the microscope, we proposed a general method that does not require any prior information. In order to compare the outcome of existing methods, different standard metrics are commonly used in literature. However, no metric is available to compare different methods in real cases. First, we validated a metric able to rank the methods as the Universal Quality Index does, but without needing any reference ground truth. Second, we proved that the approach we developed performs better in both synthetic and real cases.

Oxidation and pyrolysis of methane and methyl formate in a plug flow reactor: computational and experimenal studies

Biodiesel represents a possible substitute to the fossil fuels; for this reason a good comprehension of the kinetics involved is important. Due to the complexity of the biodiesel mixture a common practice is the use of surrogate molecules to study its reactivity. In this work are presented the experimental and computational results obtained for the oxidation and pyrolysis of methane and methyl formate conducted in a plug flow reactor. The work was divided into two parts: the first one was the setup assembly whilst, in the second one, was realized a comparison between the experimental and model results; these last was obtained using models available in literature. It was started studying the methane since, a validate model was available, in this way was possible to verify the reliability of the experimental results. After this first study the attention was focused on the methyl formate investigation. All the analysis were conducted at different temperatures, pressures and, for the oxidation, at different equivalence ratios. The results shown that, a good comprehension of the kinetics is reach but efforts are necessary to better evaluate kinetics parameters such as activation energy. The results even point out that the realized setup is adapt to study the oxidation and pyrolysis and, for this reason, it will be employed to study a longer chain esters with the aim to better understand the kinetic of the molecules that are part of the biodiesel mixture.

Phenotypic and molecular characterization of ethylene biosynthesis in apples

Ethylene plays an important role in apple fruit development. Its biosynthesis is catalyzed by two enzymes ACS and ACO. The first is considered to catalyzes the rate-limiting step of ethylene production and in apple two different alleles (MdACS1-1 and MdACS1-2) of this gene have been identified. The presence in the promoter region of MdACS1-2 allele of a SINE insertion is considered to be responsible for a low transcription level and a pronounced reduction in ethylene production in apple cultivar homozygous for this allele. However, the specific expression of each MdACS1 allele has never been reported as well as any in vivo analysis of its 5’-flanking region. With the present study we addressed these issues by developing a set of qPCR allele specific primers for MdACS1 and by a functional characterization of the MdACS1 promoters by transient expression analysis. qPCR analysis on different apple tissues and stages of development demonstrated that MdACS1-2 allele is never express and that MdACS1-1 allele is ripening-related and expresses predominantly but not exclusively in apple fruit. To test MdACS1 promoter in fruit the only protocol available in literature for transient transformation of apple fruit was evaluated and optimized. Twenty chimeric promoter::reporter constructs were generated and analyzed by Agrobacterium-transient transformation. The in vivo analysis allowed to identify an enhancer-like region of 261 bp in MdACS1 promoter and a region of 57 bp in MdACS1-2 responsible, also if not alone, in the inactivation of the MdACS1-2 allele. Through the assessment of ethylene production in a segregating progeny derived from the cross between Fuji and Mondial Gala (homozygous for MdACS1-2 allele) we demonstrated that at least two other genes may be involved in apple ethylene production. An hypothesis that could explain the difference between Fuji and Mondial Gala have been proposed.

Characterization of fold-related fractures in the carbonate rocks of the Cingoli anticline, northern Apennines, Italy

Thrust fault-related folds in carbonate rocks are characterized by deformation accommodated by different structures, such as joints, faults, pressure solution seams, and deformation bands. Defining the development of fracture systems related to the folding process is significant both for theoretical and practical purposes. Fracture systems are useful constrains in order to understand the kinematical evolution of the fold. Furthermore, understanding the relationships between folding and fracturing provides a noteworthy contribution for reconstructing the geodynamic and the structural evolution of the studied area. Moreover, as fold-related fractures influence fluid flow through rocks, fracture systems are relevant for energy production (geothermal studies, methane and CO2 , storage and hydrocarbon exploration), environmental and social issues (pollutant distribution, aquifer characterization). The PhD project shows results of a study carried out in a multilayer carbonate anticline characterized by different mechanical properties. The aim of this study is to understand the factors which influence the fracture formation and to define their temporal sequence during the folding process. The studied are is located in the Cingoli anticline (Northern Apennines), which is characterized by a pelagic multilayer characterized by sequences with different mechanical stratigraphies. A multi-scale analysis has been made in several outcrops located in different structural positions. This project shows that the conceptual sketches proposed in literature and the strain distribution models outline well the geometrical orientation of most of the set of fractures observed in the Cingoli anticline. On the other hand, the present work suggests the relevance of the mechanical stratigraphy in particular controlling the type of fractures formed (e.g. pressure solution seams, joints or shear fractures) and their subsequent evolution. Through a multi-scale analysis, and on the basis of the temporal relationship between fracture sets and their orientation respect layering, I also suggest a conceptual model for fracture systems formation.

Evaluation of Human Exposure to Magnetic Fields Generated by Electric Power Systems in Complex Configurations

The international growing concern for the human exposure to magnetic fields generated by electric power lines has unavoidably led to imposing legal limits. Respecting these limits, implies being able to calculate easily and accurately the generated magnetic field also in complex configurations. Twisting of phase conductors is such a case. The consolidated exact and approximated theory regarding a single-circuit twisted three-phase power cable line has been reported along with the proposal of an innovative simplified formula obtained by means of an heuristic procedure. This formula, although being dramatically simpler, is proven to be a good approximation of the analytical formula and at the same time much more accurate than the approximated formula found in literature. The double-circuit twisted three-phase power cable line case has been studied following different approaches of increasing complexity and accuracy. In this framework, the effectiveness of the above-mentioned innovative formula is also examined. The experimental verification of the correctness of the twisted double-circuit theoretical analysis has permitted its extension to multiple-circuit twisted three-phase power cable lines. In addition, appropriate 2D and, in particularly, 3D numerical codes for simulating real existing overhead power lines for the calculation of the magnetic field in their vicinity have been created. Finally, an innovative ‘smart’ measurement and evaluation system of the magnetic field is being proposed, described and validated, which deals with the experimentally-based evaluation of the total magnetic field B generated by multiple sources in complex three-dimensional arrangements, carried out on the basis of the measurement of the three Cartesian field components and their correlation with the field currents via multilinear regression techniques. The ultimate goal is verifying that magnetic induction intensity is within the prescribed limits.

Molekularer Magnetismus und Multistabilitäten in sternförmigen cyanidgebrückten Eisen- und Übergangsmetall-Komplexverbindungen

In der hier vorliegenden Arbeit wurden neue eisenhaltige Spincrossover-Komplexerndargestellt und deren magnetische Eigenschaften untersucht. Ausgehend von früheren Ergebnissen wurden verschiedene Strategien zur Optimierung der Eisen-Spincrossover Verbindungen verfolgt. Wie schon früher dokumentiert finden sich bei Eisen-Übergangsmetall Komplexen eine Vielzahl von Spincrossover Phänomenen. Ebenso gut dokumentiert sind die Möglichen Änderungen des Spin Zustandes durch äußere Einflüsse wie Temperatur, Druck oder Licht. Darauf aufbauend wurden nunrnverschiedene Eisenkomplexe synthetisiert und auf das Spincrossover Phänomen hin untersucht. Dazu wurden zum Einen Fe(II) Komplexe vom Typ [FeL1(NCS)2] (L1 = pmea, pmap, tepa and tmpa) betrachtet und zum anderen Sternförmige Fe(III) Komplexe vom Typ [M{(CN-FeIIIL2}x]y+. (M=Fe(II), Co(III), Mo(IV), Ru(II)) undrndodecanukleare Komplexe vom Typ [(L2Fe(III)NC)5Fe(II)CNCo(III)(CNFe(III)L2)5]4+. L2= Bis(R2,3,4 -salicylidenaminoalkyl-R1-amin. Thermischen Spincrossover und LIESST zeigen [3,3/N-H/Sal-H/Fe/Co]; [3,3/N-H/Sal-H/Fe/Ru]; [3,3/N-H/sal-H/Fe/Mo]; [3,3/N-H/Sal-H/Fe/W]; FeII(pmea)(SCN)2; thermischen Spinübergang zeigt [2,3/N-H/Sal-H/Fe/Fe-Co]. Die Ethylen gebrückten Komplexe zeigen weniger guten oder gar keinen Schalteffekt im Gegensatz zum Propylen gebrückten Komplexe. Fe(II)(PMEA)(SCN)2 zeigt vollständigen thermischen Spinübergang von High Spin nach Low Spin ein LIESST und einen LiPTH Effekt.

Raccontare, resistere. La denuncia tra novela negra e testimonio. Affinita' e differenze in tre scrittori ispanoamericani: Serna, Walsh e Bolaño.

La tesi è incentrata sui recenti sviluppi della narrativa testimoniale dell’America Latina. Verranno presi in considerazione gli ultimi contributi critici dedicati al rapporto tra finzione e realtà in letteratura, e sarà dato spazio alla costruzione narrativa della realtà e alla nascita del testimonio, come genere a sé, che raccoglie alcune delle principali opere latinoamericane degli ultimi quaranta anni. Nello specifico, l’indagine riguarderà la rappresentazione letteraria della violenza nella narrativa di denuncia di tre autori ispoanoamericani: la novela negra di Enrique Serna, il poliziesco testimoniale di Rodolfo Walsh e la scrittura estrema di Roberto Bolaño. Obiettivo della ricerca è capire in che modo i tre scrittori hanno raccontato le loro verità alternative, provando a salvaguardare la memoria, e quali effetti hanno ottenuto. Verranno analizzate non solo le tematiche affrontate, facendo riferimento quindi al contesto storico, politico e sociale al quale si rifanno, ma saranno illustrate anche le differenti tecniche di costruzione del romanzo, dell’intreccio e della trama, e verrà isolato il ruolo del testimone (diretto o indiretto) e delle fonti, per cogliere le differenze ma anche le similitudini stilistiche e narrative di ognuna delle opere. Più in generale, dimostreremo come e quanto i testi di questi autori costituiscano in realtà una forte critica al sistema imperante e diano voce alle categorie sociali altrimenti emarginate.

Diversity of the proximal femur in humans: morphological variations of the head-neck junction

The proximal femur is a high-diversity region of the human skeleton, especially at the anterior junction between head and neck, where various bony morphologies have been recognized since mid nineteenth century. Classical literature on this topic is chaotic and contradictory, making almost impossible the comparison of data from different researches. Starting from an extensive bibliographic review, the first standardized method to score these traits has been created. This method allows representing both the anatomical diversity of the region already described in literature and a part of variability not considered before, giving few and univocal definitions and allowing to collect comparable data. The method has been applied to three identified and five archaeological European skeletal collections, with the aim of investigating the distribution of these features by sex, age and side, in different places and time periods. It has also been applied to 3D digital reconstructions of femurs from CT scan files of coxo-femoral joints from fresh cadavers. In addition to the osseous traits described in the standardized method, the presence and frequency of some features known as herniation pits have been scored both on bones and on CT scans. The various osseous traits of the proximal femur are present at similar frequencies in skeletal samples from different countries and different historical periods, even if with clear local differentiation. Some of the features examined show significant trends related to their distribution by gender and age. Some hypotheses are proposed about the etiology of these morphologies and their possible implication with the acquisition of bipedalism in Humans. It is therefore highlighted the possible relation of some of these traits with the development of disorders of the hip joint. Moreover, it is not recommended the use of any of these features as a specific activity-related marker.

Turbulence models in the atmospheric boundary layer under convective conditions

In this work a modelization of the turbulence in the atmospheric boundary layer, under convective condition, is made. For this aim, the equations that describe the atmospheric motion are expressed through Reynolds averages and, then, they need closures. This work consists in modifying the TKE-l closure used in the BOLAM (Bologna Limited Area Model) forecast model. In particular, the single column model extracted from BOLAM is used, which is modified to obtain other three different closure schemes: a non-local term is added to the flux- gradient relations used to close the second order moments present in the evolution equation of the turbulent kinetic energy, so that the flux-gradient relations become more suitable for simulating an unstable boundary layer. Furthermore, a comparison among the results obtained from the single column model, the ones obtained from the three new schemes and the observations provided by the known case in literature ”GABLS2” is made.

Analysis of the introduction of a business process mapping system in Rosetti Marino spa

After a first theoric introduction about Business Process Re-engineering (BPR), are considered in particular the possible options found in literature regarding the following three macro-elements: the methodologies, the modelling notations and the tools employed for process mapping. The theoric section is the base for the analysis of the same elements into the specific case of Rosetti Marino S.p.A., an EPC contractor, operating in the Oil&Gas industry. Rosetti Marino implemented a tool developped internally in order to satisfy its needs in the most suitable way possible and buit a Map of all business processes,navigable on the Company Intranet. Moreover it adopted a methodology based upon participation, interfunctional communication and sharing. The GIGA introduction is analysed from a structural, human resources, political and symbolic point of view.

Effect of different management intensities on natural and human-induced carbon fluxes in a golf course in northern Italy

Turfgrasses are ubiquitous in urban landscape and their role on carbon (C) cycle is increasing important also due to the considerable footprint related to their management practices. It is crucial to understand the mechanisms driving the C assimilation potential of these terrestrial ecosystems Several approaches have been proposed to assess C dynamics: micro-meteorological methods, small-chamber enclosure system (SC), chrono-sequence approach and various models. Natural and human-induced variables influence turfgrasses C fluxes. Species composition, environmental conditions, site characteristics, former land use and agronomic management are the most important factors considered in literature driving C sequestration potential. At the same time different approaches seem to influence C budget estimates. In order to study the effect of different management intensities on turfgrass, we estimated net ecosystem exchange (NEE) through a SC approach in a hole of a golf course in the province of Verona (Italy) for one year. The SC approach presented several advantages but also limits related to the measurement frequency, timing and duration overtime, and to the methodological errors connected to the measuring system. Daily CO2 fluxes changed according to the intensity of maintenance, likely due to different inputs and disturbances affecting biogeochemical cycles, combined also to the different leaf area index (LAI). The annual cumulative NEE decreased with the increase of the intensity of management. NEE was related to the seasonality of turfgrass, following temperatures and physiological activity. Generally on the growing season CO2 fluxes towards atmosphere exceeded C sequestered. The cumulative NEE showed a system near to a steady state for C dynamics. In the final part greenhouse gases (GHGs) emissions due to fossil fuel consumption for turfgrass upkeep were estimated, pinpointing that turfgrass may result a considerable C source. The C potential of trees and shrubs needs to be considered to obtain a complete budget.

Topics in Local Economic Development

This thesis contributes to the current debate in literature about local economic development by considering two different topics: quality of institutions, and the role of clusters in innovation and productivity growth. The research is built upon three papers. The first paper deals with the analysis of the effect of administrative continuity on administrative efficiency. The analysis underlines the importance of different typologies of social capital. Findings reveal a positive impact on administrative efficiency (AE) by administrative continuity (AC) when it is coupled by bridging and linking social capital. On the contrary, bonding social capital influences negatively the effect by AC on AE. The second paper investigates the spatial interaction in levels of quality of government (QoG) among European regions. Notwithstanding the largely recognised role by institutions in the design of regional policies, no study has been conducted about the mechanisms of interaction and diffusion of QoG at regional level. This research wants to overcome this knowledge gap in literature. Findings reveal a heterogeneity in spatial interaction among groups of regions, i.e. ‘leader regions’ (Northern regions) and ‘lagging regions’ (Southern regions), when considering different mechanisms of interaction (learning / imitating competition and pure competition). Moreover, the effect of wealth on the levels of QoG is nonlinear. Finally, the third paper analyses the relation among specialization and productivity within the agricultural sector. In literature, the study of clusters dynamics has long neglected agriculture. The analysis describes the changes in sectorial specialization for eight main crop groups in Italian regions (NUTS 3), assessing the existence of spatial autocorrelations by using an exploratory data analysis. Furthermore, the effect of specialization on productivity is analysed within the main crop groups using a spatial panel data model. Findings reveal a marked tendency to specialization in the Italian agriculture, and a heterogeneous effect by specialization on productivity.