Caratterizzazione di membrane da nanofiltrazione

Nanofiltration (NF) is a pressure-driven membrane process, intermediate between reverse osmosis and ultrafiltration. Commercially available polymeric membranes have been used in a wide range of applications, such as drinking, process industry and waste water treatment. For all the applications requiring high stability and harsh washing procedures inorganic membranes are preferred due to their high chemical inertia. Typically, γ – Al2O3 as well as TiO2 and ZrO2 selective layers are used; the latter show higher chemical stability in a wide range of pH and temperatures. In this work the experimental characterization of two different type of membrane has been performed in order to investigate permeation properties, separation performance and efficiency with aqueous solutions containing strong inorganic electrolytes. The influence of salt concentration and feed pH as well as the role of concentration polarization and electrolyte type on the membrane behavior are investigated. Experimentation was performed testing a multi–layer structured NF membrane in α-Al2O3, TiO2 and ZrO2, and a polymeric membrane, in polyamide supported on polysulfone, with binary aqueous solutions containing NaCl, Na2SO4 or CaCl2; the effect of salt composition and pH in the feed side was studied both on flux and salt rejection. All the NF experimental data available for the two membranes were used to evaluate the volumetric membrane charge (X) corresponding to each operative conditions investigated, through the Donnan Steric Pore Model and Dielectric Exclusion (DSPM&DE). The results obtained allow to understand which are the main phenomena at the basis of the different behaviors observed.

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.

Salt stress responses in pear and quince: physiological and molecular aspects

The productivity of agricultural crops is seriously limited by salinity. This problem is rapidly increasing, particularly in irrigated lands. Like almost all the fruit tree species, Pyrus communis is generally considered a salt sensitive species, but only little information is available on its behavior under saline conditions. Previous studies, carried out in the Department of Fruit Tree and Woody Plant Science (University of Bologna), focused their attention on pear and quince salt stress responses to understand which rootstock would be the most suitable for pear in order to tolerate a salt stress condition. It has been reported that pear and quince have different ability in the uptake, translocation and accumulation of chloride (Cl-) and sodium (Na+) ions, when plants were irrigated for one season with saline water (5 dS/m). The aim of the present work was to deepen these aspects and investigate salt stress responses in pear and quince. Two different experiments have been performed: a “short-term” trial in a growth chamber and a “long-term” experiment in the open field. In the short-term experiment, three different genotypes usually adopted as pear rootstocks (MC, BA29 and Farold®40) and the pear variety Abbé Fétel own rooted have been compared under salt stress conditions. The trial was performed in a hydroponic culture system, applying a 90 mM NaCl stress to half of the plants, after five weeks of normal growth in Hoagland’s solution. During the three-weeks of salt stress treatment, physiological, mineral and molecular analyses were performed in order to monitor, for each genotype, the development of the salt stress responses in comparison with the corresponding “unstressed” plants. Farold®40 and Abbé Fétel own rooted showed the onset of leaf necrosis, due to salt toxicity, one week before quinces. Moreover, quinces displayed a significant delay in premature senescence of old leaves, while pears emerged for their ability to regenerate new leaves from apparently dead foliage with the salt stress still running. Physiological measurements, such as shoots length, chlorophyll (Chl) content, and photosynthesis, have been carried out and revealed that pears exhibited a significant reduction in water content and a wilting aspect, while for quinces a decrease in Chl content and a growth slowdown were observed. At the end of the trial, all plants were collected and organs separated for dry weight estimation and mineral analyses (Cu, Fe, Mn, Zn Mg, Ca, K, Na and Cl). Mineral contents have been affected by salinity; same macro/micro nutrients were altered in some organs or relocated within the plant. This plant response could have partially contributed to face the salt stress. Leaves and roots have been harvested for molecular analyses at four different times during stress conditions. Molecular analyses consisted of the gene expression study of three main ion transporters, well known in Arabidopsis thaliana as salt-tolerance determinants in the “SOS” pathway: NHX1 (tonoplast Na+/H+ antiporter), SOS1 (plasmalemma Na+/H+ antiporter) and HKT1 (K+ high-affinity and Na+ low-affinity transporter). These studies showed that two quince rootstocks adopted different responsive mechanisms to NaCl stress. BA29 increased its Na+ sequestration activity into leaf vacuoles, while MC enhanced temporarily the same ability, but in roots. Farold®40, instead, exhibited increases in SOS1 and HKT1 expression mainly at leaf level in the attempt to retrieve Na+ from xylem, while Abbé Fétel differently altered the expression of these genes in roots. Finally, each genotype showed a peculiar response to salt stress that was the sum of its ability in Na+ exclusion, osmotic tolerance and tissue tolerance. In the long-term experiment, potted trees of the pear variety Abbé Fétel grafted on different rootstocks (MC, BA29 and Farold®40), or own rooted and also rootstocks only were subjected to a salt stress through saline water irrigation with an electrical conductivity of 5 dS/m for two years. The purposes of this study were to evaluate salinity effects on physiological (shoot length, number of buds, photosynthesis, etc.) and yield parameters of cultivar Abbé Fétel in the different combinations and to determine the salt amount that pear is able to tolerate over the years. With this work, we confirmed the previous hypothesis that pear, despite being classified as a salt-sensitive fruit tree, can be cultivated for two years under saline water irrigation, without showing any salt toxicity symptoms or severe drawbacks on plant development and production. Among different combinations, Abbé Fétel grafted on MC resulted interesting for its peculiar behaviors under salt stress conditions. In the near future, further investigations on physiological and molecular aspects will be necessary to enrich and broaden the knowledge of salt stress responses in pear.

Effects of Resources Exploitation on Water Quality: case studies in Salt Water Intrusion and Acid Mine Drainage

Throughout the world, pressures on water resources are increasing, mainly as a result of human activity. Because of their accessibility, groundwater and surface water are the most used reservoirs. The evaluation of the water quality requires the identification of the interconnections among the water reservoirs, natural landscape features, human activities and aquatic health. This study focuses on the estimation of the water pollution linked to two different environmental issues: salt water intrusion and acid mine drainage related to the exploitation of natural resources. Effects of salt water intrusion occurring in the shallow aquifer north of Ravenna (Italy) was analysed through the study of ion- exchange occurring in the area and its variance throughout the year, applying a depth-specific sampling method. In the study area were identified ion exchange, calcite and dolomite precipitation, and gypsum dissolution and sulphate reduction as the main processes controlling the groundwater composition. High concentrations of arsenic detected only at specific depth indicate its connexion with the organic matter. Acid mine drainage effects related to the tin extraction in the Bolivian Altiplano was studied, on water and sediment matrix. Water contamination results strictly dependent on the seasonal variation, on pH and redox conditions. During the dry season the strong evaporation and scarce water flow lead to low pH values, high concentrations of heavy metals in surface waters and precipitation of secondary minerals along the river, which could be released in oxidizing conditions as demonstrated through the sequential extraction analysis. The increase of the water flow during the wet season lead to an increase of pH values and a decrease in heavy metal concentrations, due to dilution effect and, as e.g. for the iron, to precipitation.

NLGA based Active Control in Aerospace: fault tolerability, disturbance rejection, and parameter estimation

A new control scheme has been presented in this thesis. Based on the NonLinear Geometric Approach, the proposed Active Control System represents a new way to see the reconfigurable controllers for aerospace applications. The presence of the Diagnosis module (providing the estimation of generic signals which, based on the case, can be faults, disturbances or system parameters), mean feature of the depicted Active Control System, is a characteristic shared by three well known control systems: the Active Fault Tolerant Controls, the Indirect Adaptive Controls and the Active Disturbance Rejection Controls. The standard NonLinear Geometric Approach (NLGA) has been accurately investigated and than improved to extend its applicability to more complex models. The standard NLGA procedure has been modified to take account of feasible and estimable sets of unknown signals. Furthermore the application of the Singular Perturbations approximation has led to the solution of Detection and Isolation problems in scenarios too complex to be solved by the standard NLGA. Also the estimation process has been improved, where multiple redundant measuremtent are available, by the introduction of a new algorithm, here called "Least Squares - Sliding Mode". It guarantees optimality, in the sense of the least squares, and finite estimation time, in the sense of the sliding mode. The Active Control System concept has been formalized in two controller: a nonlinear backstepping controller and a nonlinear composite controller. Particularly interesting is the integration, in the controller design, of the estimations coming from the Diagnosis module. Stability proofs are provided for both the control schemes. Finally, different applications in aerospace have been provided to show the applicability and the effectiveness of the proposed NLGA-based Active Control System.