Tuzla City (BiH): an example of geohazard induced by salt extraction

Salt deposits characterize the subsurface of Tuzla (BiH) and made it famous since the ancient times. Archeological discoveries demonstrate the presence of a Neolithic pile-dwelling settlement related to the existence of saltwater springs that contributed to make the most of the area a swampy ground. Since the Roman times, the town is reported as “the City of Salt deposits and Springs”; "tuz" is the Turkish word for salt, as the Ottomans renamed the settlement in the 15th century following their conquest of the medieval Bosnia (Donia and Fine, 1994). Natural brine springs were located everywhere and salt has been evaporated by means of hot charcoals since pre-Roman times. The ancient use of salt was just a small exploitation compared to the massive salt production carried out during the 20th century by means of classical mine methodologies and especially wild brine pumping. In the past salt extraction was practised tapping natural brine springs, while the modern technique consists in about 100 boreholes with pumps tapped to the natural underground brine runs, at an average depth of 400-500 m. The mining operation changed the hydrogeological conditions enabling the downward flow of fresh water causing additional salt dissolution. This process induced severe ground subsidence during the last 60 years reaching up to 10 meters of sinking in the most affected area. Stress and strain of the overlying rocks induced the formation of numerous fractures over a conspicuous area (3 Km2). Consequently serious damages occurred to buildings and infrastructures such as water supply system, sewage networks and power lines. Downtown urban life was compromised by the destruction of more than 2000 buildings that collapsed or needed to be demolished causing the resettlement of about 15000 inhabitants (Tatić, 1979). Recently salt extraction activities have been strongly reduced, but the underground water system is returning to his natural conditions, threatening the flooding of the most collapsed area. During the last 60 years local government developed a monitoring system of the phenomenon, collecting several data about geodetic measurements, amount of brine pumped, piezometry, lithostratigraphy, extension of the salt body and geotechnical parameters. A database was created within a scientific cooperation between the municipality of Tuzla and the city of Rotterdam (D.O.O. Mining Institute Tuzla, 2000). The scientific investigation presented in this dissertation has been financially supported by a cooperation project between the Municipality of Tuzla, The University of Bologna (CIRSA) and the Province of Ravenna. The University of Tuzla (RGGF) gave an important scientific support in particular about the geological and hydrogeological features. Subsidence damage resulting from evaporite dissolution generates substantial losses throughout the world, but the causes are only well understood in a few areas (Gutierrez et al., 2008). The subject of this study is the collapsing phenomenon occurring in Tuzla area with the aim to identify and quantify the several factors involved in the system and their correlations. Tuzla subsidence phenomenon can be defined as geohazard, which represents the consequence of an adverse combination of geological processes and ground conditions precipitated by human activity with the potential to cause harm (Rosenbaum and Culshaw, 2003). Where an hazard induces a risk to a vulnerable element, a risk management process is required. The single factors involved in the subsidence of Tuzla can be considered as hazards. The final objective of this dissertation represents a preliminary risk assessment procedure and guidelines, developed in order to quantify the buildings vulnerability in relation to the overall geohazard that affect the town. The historical available database, never fully processed, have been analyzed by means of geographic information systems and mathematical interpolators (PART I). Modern geomatic applications have been implemented to deeply investigate the most relevant hazards (PART II). In order to monitor and quantify the actual subsidence rates, geodetic GPS technologies have been implemented and 4 survey campaigns have been carried out once a year. Subsidence related fractures system has been identified by means of field surveys and mathematical interpretations of the sinking surface, called curvature analysis. The comparison of mapped and predicted fractures leaded to a better comprehension of the problem. Results confirmed the reliability of fractures identification using curvature analysis applied to sinking data instead of topographic or seismic data. Urban changes evolution has been reconstructed analyzing topographic maps and satellite imageries, identifying the most damaged areas. This part of the investigation was very important for the quantification of buildings vulnerability.

Use of solvents and environmental friendly materials for applications in Green Chemistry

The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective “greenness” has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The “green” features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the “greenest” solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as “fully green” alternative solvents; however this epithet does not take into account several “brown” aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.

Fingerprint Recognition: Enhancement, Feature Extraction and Automatic Evaluation of Algorithms

The identification of people by measuring some traits of individual anatomy or physiology has led to a specific research area called biometric recognition. This thesis is focused on improving fingerprint recognition systems considering three important problems: fingerprint enhancement, fingerprint orientation extraction and automatic evaluation of fingerprint algorithms. An effective extraction of salient fingerprint features depends on the quality of the input fingerprint. If the fingerprint is very noisy, we are not able to detect a reliable set of features. A new fingerprint enhancement method, which is both iterative and contextual, is proposed. This approach detects high-quality regions in fingerprints, selectively applies contextual filtering and iteratively expands like wildfire toward low-quality ones. A precise estimation of the orientation field would greatly simplify the estimation of other fingerprint features (singular points, minutiae) and improve the performance of a fingerprint recognition system. The fingerprint orientation extraction is improved following two directions. First, after the introduction of a new taxonomy of fingerprint orientation extraction methods, several variants of baseline methods are implemented and, pointing out the role of pre- and post- processing, we show how to improve the extraction. Second, the introduction of a new hybrid orientation extraction method, which follows an adaptive scheme, allows to improve significantly the orientation extraction in noisy fingerprints. Scientific papers typically propose recognition systems that integrate many modules and therefore an automatic evaluation of fingerprint algorithms is needed to isolate the contributions that determine an actual progress in the state-of-the-art. The lack of a publicly available framework to compare fingerprint orientation extraction algorithms, motivates the introduction of a new benchmark area called FOE (including fingerprints and manually-marked orientation ground-truth) along with fingerprint matching benchmarks in the FVC-onGoing framework. The success of such framework is discussed by providing relevant statistics: more than 1450 algorithms submitted and two international competitions.

General effective medium model for the complex permittivity extraction with an open-ended coaxial probe in presence of a multilayer material under test

The work presented in this thesis is focused on the open-ended coaxial-probe frequency-domain reflectometry technique for complex permittivity measurement at microwave frequencies of dispersive dielectric multilayer materials. An effective dielectric model is introduced and validated to extend the applicability of this technique to multilayer materials in on-line system context. In addition, the thesis presents: 1) a numerical study regarding the imperfectness of the contact at the probe-material interface, 2) a review of the available models and techniques, 3) a new classification of the extraction schemes with guidelines on how they can be used to improve the overall performance of the probe according to the problem requirements.

Topics in financial econometrics

In the first chapter, we consider the joint estimation of objective and risk-neutral parameters for SV option pricing models. We propose a strategy which exploits the information contained in large heterogeneous panels of options, and we apply it to S&P 500 index and index call options data. Our approach breaks the stochastic singularity between contemporaneous option prices by assuming that every observation is affected by measurement error. We evaluate the likelihood function by using a MC-IS strategy combined with a Particle Filter algorithm. The second chapter examines the impact of different categories of traders on market transactions. We estimate a model which takes into account traders’ identities at the transaction level, and we find that the stock prices follow the direction of institutional trading. These results are carried out with data from an anonymous market. To explain our estimates, we examine the informativeness of a wide set of market variables and we find that most of them are unambiguously significant to infer the identity of traders. The third chapter investigates the relationship between the categories of market traders and three definitions of financial durations. We consider trade, price and volume durations, and we adopt a Log-ACD model where we include information on traders at the transaction level. As to trade durations, we observe an increase of the trading frequency when informed traders and the liquidity provider intensify their presence in the market. For price and volume durations, we find the same effect to depend on the state of the market activity. The fourth chapter proposes a strategy to express order aggressiveness in quantitative terms. We consider a simultaneous equation model to examine price and volume aggressiveness at Euronext Paris, and we analyse the impact of a wide set of order book variables on the price-quantity decision.

Valorization of pomaces from the mechanical extraction of virgin olive oils in dairy animal feeding

This research work is aimed at the valorization of two types of pomace deriving from the extra virgin olive oil mechanical extraction process, such as olive pomace and a new by-product named “paté”, in the livestock sector as important sources of antioxidants and unsaturated fatty acids. In the first research the suitability of dried stoned olive pomace as a dietary supplement for dairy buffaloes was evaluated. The effectiveness of this utilization in modifying fatty acid composition and improving the oxidative stability of buffalo milk and mozzarella cheese have been proven by means of the analysis of qualitative and quantitative parameters. In the second research the use of paté as a new by-product in dietary feed supplementation for dairy ewes, already fed with a source of unsaturated fatty acids such as extruded linseed, was studied in order to assess the effect of this combination on the dairy products obtained. The characterization of paté as a new by-product was also carried out, studying the optimal conditions of its stabilization and preservation at the same time. The main results, common to both researches, have been the detection and the characterization of hydrophilic phenols in the milk. The analytical detection of hydroxytyrosol and tyrosol in the ewes’ milk fed with the paté and hydroxytyrosol in buffalo fed with pomace showed for the first time the presence in the milk of hydroxytyrosol, which is one of the most important bioactive compounds of the oil industry products; the transfer of these antioxidants and the proven improvement of the quality of milk fat could positively interact in the prevention of some human cardiovascular diseases and some tumours, increasing in this manner the quality of dairy products, also improving their shelf-life. These results also provide important information on the bioavailability of these phenolic compounds.

Knowledge Patterns for the Web: extraction, tranformation and reuse

This thesis aims at investigating methods and software architectures for discovering what are the typical and frequently occurring structures used for organizing knowledge in the Web. We identify these structures as Knowledge Patterns (KPs). KP discovery needs to address two main research problems: the heterogeneity of sources, formats and semantics in the Web (i.e., the knowledge soup problem) and the difficulty to draw relevant boundary around data that allows to capture the meaningful knowledge with respect to a certain context (i.e., the knowledge boundary problem). Hence, we introduce two methods that provide different solutions to these two problems by tackling KP discovery from two different perspectives: (i) the transformation of KP-like artifacts to KPs formalized as OWL2 ontologies; (ii) the bottom-up extraction of KPs by analyzing how data are organized in Linked Data. The two methods address the knowledge soup and boundary problems in different ways. The first method provides a solution to the two aforementioned problems that is based on a purely syntactic transformation step of the original source to RDF followed by a refactoring step whose aim is to add semantics to RDF by select meaningful RDF triples. The second method allows to draw boundaries around RDF in Linked Data by analyzing type paths. A type path is a possible route through an RDF that takes into account the types associated to the nodes of a path. Then we present K~ore, a software architecture conceived to be the basis for developing KP discovery systems and designed according to two software architectural styles, i.e, the Component-based and REST. Finally we provide an example of reuse of KP based on Aemoo, an exploratory search tool which exploits KPs for performing entity summarization.

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.

Secondary Microseisms Characterization and Green’s Function Extraction at the Larderello-Travale Geothermal Field (Italy)

Over the past ten years, the cross-correlation of long-time series of ambient seismic noise (ASN) has been widely adopted to extract the surface-wave part of the Green’s Functions (GF). This stochastic procedure relies on the assumption that ASN wave-field is diffuse and stationary. At frequencies <1Hz, the ASN is mainly composed by surface-waves, whose origin is attributed to the sea-wave climate. Consequently, marked directional properties may be observed, which call for accurate investigation about location and temporal evolution of the ASN-sources before attempting any GF retrieval. Within this general context, this thesis is aimed at a thorough investigation about feasibility and robustness of the noise-based methods toward the imaging of complex geological structures at the local (∼10-50km) scale. The study focused on the analysis of an extended (11 months) seismological data set collected at the Larderello-Travale geothermal field (Italy), an area for which the underground geological structures are well-constrained thanks to decades of geothermal exploration. Focusing on the secondary microseism band (SM;f>0.1Hz), I first investigate the spectral features and the kinematic properties of the noise wavefield using beamforming analysis, highlighting a marked variability with time and frequency. For the 0.1-0.3Hz frequency band and during Spring- Summer-time, the SMs waves propagate with high apparent velocities and from well-defined directions, likely associated with ocean-storms in the south- ern hemisphere. Conversely, at frequencies >0.3Hz the distribution of back- azimuths is more scattered, thus indicating that this frequency-band is the most appropriate for the application of stochastic techniques. For this latter frequency interval, I tested two correlation-based methods, acting in the time (NCF) and frequency (modified-SPAC) domains, respectively yielding esti- mates of the group- and phase-velocity dispersions. Velocity data provided by the two methods are markedly discordant; comparison with independent geological and geophysical constraints suggests that NCF results are more robust and reliable.

Non Invasive Tools for Early Detection of Autism Spectrum Disorders

Autism Spectrum Disorders (ASDs) describe a set of neurodevelopmental disorders. ASD represents a significant public health problem. Currently, ASDs are not diagnosed before the 2nd year of life but an early identification of ASDs would be crucial as interventions are much more effective than specific therapies starting in later childhood. To this aim, cheap an contact-less automatic approaches recently aroused great clinical interest. Among them, the cry and the movements of the newborn, both involving the central nervous system, are proposed as possible indicators of neurological disorders. This PhD work is a first step towards solving this challenging problem. An integrated system is presented enabling the recording of audio (crying) and video (movements) data of the newborn, their automatic analysis with innovative techniques for the extraction of clinically relevant parameters and their classification with data mining techniques. New robust algorithms were developed for the selection of the voiced parts of the cry signal, the estimation of acoustic parameters based on the wavelet transform and the analysis of the infant’s general movements (GMs) through a new body model for segmentation and 2D reconstruction. In addition to a thorough literature review this thesis presents the state of the art on these topics that shows that no studies exist concerning normative ranges for newborn infant cry in the first 6 months of life nor the correlation between cry and movements. Through the new automatic methods a population of control infants (“low-risk”, LR) was compared to a group of “high-risk” (HR) infants, i.e. siblings of children already diagnosed with ASD. A subset of LR infants clinically diagnosed as newborns with Typical Development (TD) and one affected by ASD were compared. The results show that the selected acoustic parameters allow good differentiation between the two groups. This result provides new perspectives both diagnostic and therapeutic.