Perfluoroalkylated substances in food matrices: development of mass spectrometry based analytical methods and preliminary monitoring

Perfluoroalkylated substances are a group of chemicals that have been largely employed during the last 60 years in several applications, widely spreading and accumulating in the environment due to their extreme resistance to degradation. As a consequence, they have been found also in various types of food as well as in drinking water, proving that they can easily reach humans through the diet. The available information concerning their adverse effects on health has recently increased the interest towards these contaminants and highlighted the importance of investigating all the potential sources of human exposure, among which diet was proved to be the most relevant. This need has been underlined by the European Union through Recommendation 2010/161/EU: in this document, Member States were called to monitor their presence of in food, producing accurate estimations of human exposure. The purpose of the research presented in this thesis, which is the result of a partnership between an Italian and a French laboratory, was to develop reliable tools for the analysis of these pollutants in food, to be used for generating data on potentially contaminated matrices. An efficient method based on liquid chromatography-mass spectrometry for the detection of 16 different perfluorinated compounds in milk has been validated in accordance with current European regulation guidelines (2002/657/EC) and is currently under evaluation for ISO 17025 accreditation. The proposed technique was applied to cow, powder and human breast milk samples from Italy and France to produce a preliminary monitoring on the presence of these contaminants. In accordance with the above mentioned European Recommendation, this project led also to the development of a promising technique for the quantification of some precursors of these substances in fish. This method showed extremely satisfying performances in terms of linearity and limits of detection, and will be useful for future surveys.

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.

In situ real-time investigation of Organic Ultra-Thin-Film transistors: growth, electrical properties and biosensing applications

Organic electronics has grown enormously during the last decades driven by the encouraging results and the potentiality of these materials for allowing innovative applications, such as flexible-large-area displays, low-cost printable circuits, plastic solar cells and lab-on-a-chip devices. Moreover, their possible field of applications reaches from medicine, biotechnology, process control and environmental monitoring to defense and security requirements. However, a large number of questions regarding the mechanism of device operation remain unanswered. Along the most significant is the charge carrier transport in organic semiconductors, which is not yet well understood. Other example is the correlation between the morphology and the electrical response. Even if it is recognized that growth mode plays a crucial role into the performance of devices, it has not been exhaustively investigated. The main goal of this thesis was the finding of a correlation between growth modes, electrical properties and morphology in organic thin-film transistors (OTFTs). In order to study the thickness dependence of electrical performance in organic ultra-thin-film transistors, we have designed and developed a home-built experimental setup for performing real-time electrical monitoring and post-growth in situ electrical characterization techniques. We have grown pentacene TFTs under high vacuum conditions, varying systematically the deposition rate at a fixed room temperature. The drain source current IDS and the gate source current IGS were monitored in real-time; while a complete post-growth in situ electrical characterization was carried out. At the end, an ex situ morphological investigation was performed by using the atomic force microscope (AFM). In this work, we present the correlation for pentacene TFTs between growth conditions, Debye length and morphology (through the correlation length parameter). We have demonstrated that there is a layered charge carriers distribution, which is strongly dependent of the growth mode (i.e. rate deposition for a fixed temperature), leading to a variation of the conduction channel from 2 to 7 monolayers (MLs). We conciliate earlier reported results that were apparently contradictory. Our results made evident the necessity of reconsidering the concept of Debye length in a layered low-dimensional device. Additionally, we introduce by the first time a breakthrough technique. This technique makes evident the percolation of the first MLs on pentacene TFTs by monitoring the IGS in real-time, correlating morphological phenomena with the device electrical response. The present thesis is organized in the following five chapters. Chapter 1 makes an introduction to the organic electronics, illustrating the operation principle of TFTs. Chapter 2 presents the organic growth from theoretical and experimental points of view. The second part of this chapter presents the electrical characterization of OTFTs and the typical performance of pentacene devices is shown. In addition, we introduce a correcting technique for the reconstruction of measurements hampered by leakage current. In chapter 3, we describe in details the design and operation of our innovative home-built experimental setup for performing real-time and in situ electrical measurements. Some preliminary results and the breakthrough technique for correlating morphological and electrical changes are presented. Chapter 4 meets the most important results obtained in real-time and in situ conditions, which correlate growth conditions, electrical properties and morphology of pentacene TFTs. In chapter 5 we describe applicative experiments where the electrical performance of pentacene TFTs has been investigated in ambient conditions, in contact to water or aqueous solutions and, finally, in the detection of DNA concentration as label-free sensor, within the biosensing framework.

Towards Rapid Environmental Assessment and Coastal Forecasting in the Northern Adriatic Sea

A new Coastal Rapid Environmental Assessment (CREA) strategy has been developed and successfully applied to the Northern Adriatic Sea. CREA strategy exploits the recent advent of operational oceanography to establish a CREA system based on an operational regional forecasting system and coastal monitoring networks of opportunity. The methodology wishes to initialize a coastal high resolution model, nested within the regional forecasting system, blending the large scale parent model fields with the available coastal observations to generate the requisite field estimates. CREA modeling system consists of a high resolution, O(800m), Adriatic SHELF model (ASHELF) implemented into the Northern Adriatic basin and nested within the Adriatic Forecasting System (AFS) (Oddo et al. 2006). The observational system is composed by the coastal networks established in the framework of ADRICOSM (ADRiatic sea integrated COastal areaS and river basin Managment system) Pilot Project. An assimilation technique exerts a correction of the initial field provided by AFS on the basis of the available observations. The blending of the two data sets has been carried out through a multi-scale optimal interpolation technique developed by Mariano and Brown (1992). Two CREA weekly exercises have been conducted: the first, at the beginning of May (spring experiment); the second in middle August (summer experiment). The weeks have been chosen looking at the availability of all coastal observations in the initialization day and one week later to validate model results, verifying our predictive skills. ASHELF spin up time has been investigated too, through a dedicated experiment, in order to obtain the maximum forecast accuracy within a minimum time. Energetic evaluations show that for the Northern Adriatic Sea and for the forcing applied, a spin-up period of one week allows ASHELF to generate new circulation features enabled by the increased resolution and its total kinetic energy to establish a new dynamical balance. CREA results, evaluated by mean of standard statistics between ASHELF and coastal CTDs, show improvement deriving from the initialization technique and a good model performance in the coastal areas of the Northern Adriatic basin, characterized by a shallow and wide continental shelf subject to substantial freshwater influence from rivers. Results demonstrate the feasibility of our CREA strategy to support coastal zone management and wish an additional establishment of operational coastal monitoring activities to advance it.

Magma injections and destabilization of basaltic volcanoes: a numerical study. Application to La Reunion (Indian ocean, France) and Stromboli (Tyrrhenian sea, Italy)

Most basaltic volcanoes are affected by recurrent lateral instabilities during their evolution. Numerous factors have been shown to be involved in the process of flank destabilization occurring over long periods of time or by instantaneous failures. However, the role of these factors on the mechanical behaviour and stability of volcanic edifices is poorly-constrained as lateral failure usually results from the combined effects of several parameters. Our study focuses on the morphological and structural comparison of two end-member basaltic systems, La Reunion (Indian ocean, France) and Stromboli (southern Tyrrhenian sea, Italy). We showed that despite major differences on their volumes and geodynamic settings, both systems present some similarities as they are characterized by an intense intrusive activity along well-developed rift zones and recurrent phenomena of flank collapse during their evolution. Among the factors of instability, the examples of la Reunion and Stromboli evidence the major contribution of intrusive complexes to volcano growth and destruction as attested by field observations and the monitoring of these active volcanoes. Classical models consider the relationship between vertical intrusions of magma and flank movements along a preexisting sliding surface. A set of published and new field data from Piton des Neiges volcano (La Reunion) allowed us to recognize the role of subhorizontal intrusions in the process of flank instability and to characterize the geometry of both subvertical and subhorizontal intrusions within basaltic edifices. This study compares the results of numerical modelling of the displacements associated with high-angle and low-angle intrusions within basaltic volcanoes. We use a Mixed Boundary Element Method to investigate the mechanical response of an edifice to the injection of magmatic intrusions in different stress fields. Our results indicate that the anisotropy of the stress field favours the slip along the intrusions due to cointrusive shear stress, generating flank-scale displacements of the edifice, especially in the case of subhorizontal intrusions, capable of triggering large-scale flank collapses on basaltic volcanoes. Applications of our theoretical results to real cases of flank displacements on basaltic volcanoes (such as the 2007 eruptive crisis at La Reunion and Stromboli) revealed that the previous model of subvertical intrusions-related collapse is a likely mechanism affecting small-scale steeply-sloping basaltic volcanoes like Stromboli. Furthermore, our field study combined to modelling results confirms the importance of shallow-dipping intrusions in the morpho-structural evolution of large gently-sloping basaltic volcanoes like Piton de la Fournaise, Etna and Kilauea, with particular regards to flank instability, which can cause catastrophic tsunamis.

Poverty and Mental Health. Tangible and Intangible Aspects of Microcredit

Microcredit, a small lending system, invests on an individual's creativity by stimulating the development of their own potential. This process leads to the attainment of various objectives which in turn allow individuals to develop their skill awareness. Consequently, this process also increases an individual’s self-esteem and self-confidence. These factors play an important role in the aetiology of a number of mental disorders. Namely, those characterized by a series of psychological conditions which impede the full development of a person’s personal, relational and social sphere. Furthermore, since Microcredit is thought to produce tangible goods, such as income, and intangible goods, such as self-esteem and mutual trust, it could also represent an innovative socio-economic tool. We therefore also hypothesize that, Microcredit would be valuable in maximizing abilities/skills in those subjects who are financially excluded and rarely perceived as a ‘resource’ for the Community The longitudinal study set the impact of the Grameen Bank microcredit program on new borrowers women from Noakhali District at the south Bangladesh. The impact evaluation assessment has been structured to detect individual, family and social changes. Manova Analysis allowed distinguishing from women with positive or negative outcomes related to the loan performance. Data revealed consistent differences in terms of economical outcomes and psychological well being amongst the groups of subject analyzed. The data gathered in relation to the changes arisen in the individuals should be looked into through future, continuous and systematic, monitoring.

Experimental assessment of environmental decay effects in masonry via non destructive diagnostic techniques and mechanical tests

Environmental decay in porous masonry materials, such as brick and mortar, is a widespread problem concerning both new and historic masonry structures. The decay mechanisms are quite complex dependng upon several interconnected parameters and from the interaction with the specific micro-climate. Materials undergo aesthetical and substantial changes in character but while many studies have been carried out, the mechanical aspect has been largely understudied while it bears true importance from the structural viewpoint. A quantitative assessment of the masonry material degradation and how it affects the load-bearing capacity of masonry structures appears missing. The research work carried out, limiting the attention to brick masonry addresses this issue through an experimental laboratory approach via different integrated testing procedures, both non-destructive and mechanical, together with monitoring methods. Attention was focused on transport of moisture and salts and on the damaging effects caused by the crystallization of two different salts, sodium chloride and sodium sulphate. Many series of masonry specimens, very different in size and purposes were used to track the damage process since its beginning and to monitor its evolution over a number of years Athe same time suitable testing techniques, non-destructive, mini-invasive, analytical, of monitoring, were validated for these purposes. The specimens were exposed to different aggressive agents (in terms of type of salt, of brine concentration, of artificial vs. open-air natural ageing, …), tested by different means (qualitative vs. quantitative, non destructive vs. mechanical testing, punctual vs. wide areas, …), and had different size (1-, 2-, 3-header thick walls, full-scale walls vs. small size specimens, brick columns and triplets vs. small walls, masonry specimens vs. single units of brick and mortar prisms, …). Different advanced testing methods and novel monitoring techniques were applied in an integrated holistic approach, for quantitative assessment of masonry health state.