Il deperimento dei geomateriali da costruzione: implicazioni sulla capacità sismica residua di edifici in CA e muratura ordinaria

This work is dedicated to the study of damaging phenomena involving reinforced concrete structures and masonry buildings and the consequences in terms of structural performances decay. In the Italian context there are many examples of structures that have already exceeded their service life, considering not only the ancient buildings but also infrastructures and R/C buildings that today are operating from more than 50th years. Climate change which is subject to the entire planet, with changing in seasonal weather and increasing in environmental pollution, is not excluded could have a harmful influence on the rate of building materials decay previously deemed as durables. If the aggressive input changes very fast, for example in a few decades, then it can also change the response of a construction material considered so far durable; in this way the knowledge about the art of good build, consolidated over the centuries, is thwarted. Hence this study is focused on the possibility to define the residual capacity for vertical or seismic loads for structures that are already at the limit of their service life, or for which is impossible to define a service life. The problem in an analysis of this kind, and that is what makes this research different from the main studies avaibles in the literature, is to keep in correlation – in a not so expensive computationally way – issues such as: - dangerous environmental inputs adequately simulated; - environmental conditions favorable to the spread of pollutants and development of the degradation reactions (decay’s speed); - link between environmental degradation and residual bearing capacity A more realistic assessment of materials residual performances that constitute the structure allows to leave the actual system for the residual load-bearing capacity estimation in which all factors are simply considered through the use of a safety factor on the materials properties.

The Law and Economics of Eco-labels

Eco-labels and certification are one of the many environmental policy tools that have been under scrutiny in recent years. This is because the damages of environmental degradation are becoming more apparent over time. Hence there is a pressure to come up with tools that help solve even small parts of the problem. Eco-labels have been around for over 30 years. However the market, the environment and eco-labels have changed drastically during this period. Moreover, in the last 5 years there has been a sudden increase in eco-labels making them more visible in the market and to the average consumer. All this has made evident that little is known about the effectiveness of eco-labels as environmental policy tools. Hence, there is a call to find answers regarding the actual effects of eco-labels on the market and on the environment. While this work cannot address whether eco-labels have an environmental impact it addresses the effects of eco-labels on the markets. Moreover, this work aimed to find the role of law in eco-labelling. In addition, it aims to find a legal solution that would improve the performance of eco-labelling and certification.

Life Cycle Thinking for sustainability assessment and decision-making in selected food supply chains in Costa Rica

The Agenda 2030 contains 17 integrated Sustainable Development Goals (SDGs). SDG 12 for Sustainable Consumption and Production (SCP) promotes the efficient use of resources through a systemic change that decouples economic growth from environmental degradation. The Food Systems (FS) pillar in SDG 12 entails paramount relevance due to its interconnection to many other SDGs, and even when being a crucial world food supplier, the Latin American and Caribbean (LAC) Region struggles with environmental and social externalities, low investment in agriculture, inequity, food insecurity, poverty, and migration. Life Cycle Thinking (LCT) was regarded as a pertinent approach to identify hotspots and trade-offs, and support decision-making process to aid LAC Region countries as Costa Rica to diagnose sustainability and overcome certain challenges. This thesis aimed to ‘evaluate the sustainability of selected products from food supply chains in Costa Rica, to provide inputs for further sustainable decision-making, through the application of Life Cycle Thinking’. To do this, Life Cycle Assessment (LCA), Life Cycle Costing (LCC), and Social Life Cycle Assessment (S-LCA) evaluated the sustainability of food-waste-to-energy alternatives, and the production of green coffee, raw milk and leafy vegetables, and identified environmental, social and cost hotspots. This approach also proved to be a useful component of decision-making and policy-making processes together with other methods. LCT scientific literature led by LAC or Costa Rican researchers is still scarce; therefore, this research contributed to improve capacities in the use of LCT in this context, while offering potential replicability of the developed frameworks in similar cases. Main limitations related to the representativeness and availability of primary data; however, future research and extension activities are foreseen to increase local data availability, capacity building, and the discussion of potential integration through Life Cycle Sustainability Assessment (LCSA).

On the degradation mechanisms under the influence of pedological factors through the study of archeological bronze patina

This experimental thesis concerns the study of the long-term behaviour of ancient bronzes recently excavated from burial conditions. The scientific interest is to clarify the effect of soil parameters on the degradation mechanisms of ancient bronze alloy. The work took into consideration bronzes recovered from the archaeological sites in the region of Dobrudja, Romania. The first part of research work was dedicated to the characterization of bronze artefacts using non destructive (micro-FTIR, reflectance mode) and micro-destructive (based on sampling and analysis of a stratigraphical section by OM and SEM-EDX) methods. Burial soils were geologically classified and analyzed by chemical methods (pH, conductivity, anions content). Most of objects analyzed showed a coarse and inhomogeneous corroded structure, often made up of several corrosion layers. This has been explained by the silt nature of soils, which contain low amount of clay and are, therefore, quite accessible to water and air. The main cause of a high dissolution rate of bronze alloys is the alternate water saturation and instauration of the soil, for example on a seasonal scale. Moreover, due to the vicinity of the Black Sea, the detrimental effect of chlorine has been evidenced for few objects, which were affected by the bronze disease. A general classification of corrosion layers was achieved by comparing values of the ratio Cu/Sn in the alloy and in the patina. Decuprification is a general trend, and enrichment of copper within the corrosion layers, due to the formation of thick layers of cuprite (Cu2O), is pointed out as well. Uncommon corrosion products and degradation patterns were presented as well, and they are probably due to peculiar local conditions taking place during the burial time, such as anaerobic conditions or fluctuating environmental conditions. In order to acquire a better insight into the corrosion mechanisms, the second part of the thesis has regarded simulation experiments, which were conducted on commercial Cu-Sn alloys, whose composition resembles those of ancient artefacts one. Electrochemical measurements were conducted in natural electrolytes, such as solutions extracted from natural soil (sampled at the archaeological sites) and seawater. Cyclic potentiodynamic experiments allowed appreciating the mechanism of corrosion in both cases. Soil extract’s electrolyte has been evaluated being a non aggressive medium, while artificial solution prepared by increasing the concentration of anions caused the pitting corrosion of the alloy, which is demonstrated by optical observations. In particular, electrochemical impedance spectroscopy allows assessing qualitatively the nature of corroded structures formed in soil and seawater. A double-structured layer is proposed, which differ, in the two cases, for the nature of the internal passive layer, which result defectiveness and porous in case of seawater.

Archaeological Baltic amber: degradation mechanisms and conservation measures

The aim of this project was to achieve a deep understanding of the mechanisms by which Baltic amber degrades, in order to develop techniques for preventive conservation of archaeological amber objects belonging to the National Museum of Denmark’s collections. To examine deterioration of Baltic amber, a starting point was to identify and monitor surface and bulk properties which are affected during degradation. The way to operate consisted of the use of accelerated ageing to initiate degradation of raw Baltic amber samples in different conditions of relative humidity, oxygen exposure or pH and, successively, of the use of non/micro-destructive techniques to identify and quantify changes in visual, chemical and structural properties. A large piece of raw Baltic amber was used to prepare several test samples for two different kinds of accelerated ageing: thermal-ageing and photo-ageing. During the ageing, amber samples were regularly examined through several analytical techniques related to different information: appearance/colour change by visual examination, photography and colorimetry; chemical change by infrared spectroscopy, Raman spectroscopy and elemental analysis; rate of oxidation by oxygen measurement; qualitative analysis of released volatiles by gas chromatography – mass spectrometry. The obtained results were analysed through both critical evaluation and statistical study. After the interpretation of the achieved data, the main relations between amber and environmental factors during the degradation process became clearer and it was possible to identify the major pathways by which amber degrades, such as hydrolysis of esters into alcohols and carboxylic acids, thermal-oxidation and photo-oxidation of terpenoid components, depolymerisation and decomposition of the chemical structure. At the end it was possible to suggest a preventive conservation strategy based on the control of climatic, atmospheric and lighting parameters in the environment where Baltic amber objects are stored and displayed.

Environmental weathering of natural and artificial stones used in historical architecture: influence of microstructure and new restoration methods

For some study cases (the Cathedral of Modena, Italy, XII-XIV century; the Ducal Palace in Mantua, Italy, XVI century; the church of San Francesco in Fano, Italy, XIV-XIX century), considered as representative of the use of natural and artificial stones in historical architecture, the complex interaction between environ-mental aggressiveness, materials’ microstructural characteristics and degradation was investigated. From the results of such analyses, it was found that materials microstructure plays a fundamental role in the actual extent to which weathering mechanisms affect natural and artificial stones. Consequently, the need of taking into account the important role of material microstructure, when evaluating the environmental aggressiveness to natural and artificial stones, was highlighted. Therefore, a possible quantification of the role of microstructure on the resistance to environmental attack was investigated. By exposing stone samples, with significantly different microstructural features, to slightly acidic aqueous solutions, simulating clean and acid rain, a good correlation between weight losses and the product of carbonate content and specific surface area (defined as the “vulnerable specific surface area”) was found. Alongside the evaluation of stone vulnerability, the development of a new consolidant for weathered carbonate stones was undertaken. The use of hydroxya-patite, formed by reacting the calcite of the stone with an aqueous solution of di-ammonium hydrogen phosphate, was found to be a promising consolidating tech-nique for carbonates stones. Indeed, significant increases in the mechanical prop-erties can be achieved after the treatment, which has the advantage of simply con-sisting in a non-hazardous aqueous solution, able to penetrate deeply into the stone (> 2 cm) and bring significant strengthening after just 2 days of reaction. Furthermore, the stone sorptivity is not eliminated after treatment, so that water and water vapor exchanges between the stone and the environment are not com-pletely blocked.

Pyrolysis of peptides and proteins. Analytical study and environmental applications

Analytical pyrolysis was used to investigate the formation of diketopiperazines (DKPs) which are cyclic dipeptides formed from the thermal degradation of proteins. A quali/quantitative procedure was developed combining microscale flash pyrolysis at 500 °C with gas chromatography-mass spectrometry (GC-MS) of DKPs trapped onto an adsorbent phase. Polar DKPs were silylated prior to GC-MS. Particular attention was paid to the identification of proline (Pro) containing DKPs due to their greater facility of formation. The GC-MS characteristics of more than 80 original and silylated DKPs were collected from the pyrolysis of sixteen linear dipeptides and four model proteins (e.g. bovine serum albumin, BSA). The structure of a novel DKP, cyclo(pyroglutamic-Pro) was established by NMR and ESI-MS analysis, while the structures of other novel DKPs remained tentative. DKPs resulted rather specific markers of amino acid sequence in proteins, even though the thermal degradation of DKPs should be taken into account. Structural information of DKPs gathered from the pyrolysis of model compounds was employed to the identification of these compounds in the pyrolysate of proteinaceous samples, including intrinsecally unfolded protein (IUP). Analysis of the liquid fraction (bio-oil) obtained from the pyrolysis of microalgae Nannochloropsis gaditana, Scenedesmus spp with a bench scale reactor showed that DKPs constituted an important pool of nitrogen-containing compounds. Conversely, the level of DKPs was rather low in the bio-oil of Botryococcus braunii. The developed micropyrolysis procedure was applied in combination with thermogravimetry (TGA) and infrared spectroscopy (FT-IR) to investigate surface interaction between BSA and synthetic chrysotile. The results showed that the thermal behavior of BSA (e.g. DKPs formation) was affected by the different form of doped synthetic chrysotile. The typical DKPs evolved from collagen were quantified in the pyrolysates of archaeological bones from Vicenne Necropolis in order to evaluate their conservation status in combination with TGA, FTIR and XRD analysis.

Novel etheroatom containing aliphatic polyesters for biomedical and environmental applications

Biodegradable polymers for short time applications have attracted much interest all over the world. The reason behind this growing interest is the incompatibility of the polymeric wastes with the environment where they are disposed after usage. Synthetic aliphatic polyesters represent one of the most economically competitive biodegradable polymers. In addition, they gained considerable attention as they combine biodegradability and biocompatibility with interesting physical and chemical properties. In this framework, the present research work focused on the modification by reactive blending and polycondensation of two different aliphatic polyesters, namely poly(butylene succinate) (PBS) and poly(butylene 1,4-cyclohexanedicarboxylate) (PBCE). Both are characterized by good thermal properties, but their mechanical characteristics do not fit the requirements for applications in which high flexibility is requested and, moreover, both show slow biodegradation rate. With the aim of developing new materials with improved characteristics with respect to the parent homopolymers, novel etheroatom containing PBS and PBCE-based fully aliphatic polyesters and copolyesters have been therefore synthesized and carefully characterized. The introduction of oxygen or sulphur atoms along the polymer chains, by acting on chemical composition or molecular architecture, tailored solid-state properties and biodegradation rate: type and amount of comonomeric units and sequence distribution deeply affected the material final properties owing, among all, to the hydrophobic/hydrophilic ratio and to the different ability of the polymer to crystallize. The versatility of the synthesized copolymers has been well proved: as a matter of fact these polymers can be exploited both for biomedical and ecological applications. Feasibility of 3D electrospun scaffolds has been investigated, biocompatibility studies and controlled release of a model molecule showed good responses. As regards ecological applications, barrier properties and eco-toxicological assessments have been conducted with outstanding results. Finally, the ability of the novel polyesters to undergo both hydrolytic and enzymatic degradation has been demonstrated under physiological and environmental conditions.

Stream sediments analysis for geochemical mapping of Romagna Apennines (Northern Italy): monitoring and management tool of environmental resources at various scales

Geochemical mapping is a valuable tool for the control of territory that can be used not only in the identification of mineral resources and geological, agricultural and forestry studies but also in the monitoring of natural resources by giving solutions to environmental and economic problems. Stream sediments are widely used in the sampling campaigns carried out by the world's governments and research groups for their characteristics of broad representativeness of rocks and soils, for ease of sampling and for the possibility to conduct very detailed sampling In this context, the environmental role of stream sediments provides a good basis for the implementation of environmental management measures, in fact the composition of river sediments is an important factor in understanding the complex dynamics that develop within catchment basins therefore they represent a critical environmental compartment: they can persistently incorporate pollutants after a process of contamination and release into the biosphere if the environmental conditions change. It is essential to determine whether the concentrations of certain elements, in particular heavy metals, can be the result of natural erosion of rocks containing high concentrations of specific elements or are generated as residues of human activities related to a certain study area. This PhD thesis aims to extract from an extensive database on stream sediments of the Romagna rivers the widest spectrum of informations. The study involved low and high order stream in the mountain and hilly area, but also the sediments of the floodplain area, where intensive agriculture is active. The geochemical signals recorded by the stream sediments will be interpreted in order to reconstruct the natural variability related to bedrock and soil contribution, the effects of the river dynamics, the anomalous sites, and with the calculation of background values be able to evaluate their level of degradation and predict the environmental risk.

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.

Nanocomposites based on poly(caprolactone)-chitosan electrospun nanofibers and metallic oxide nanoparticles. Their potential use to adsorption and photocatalytic degradation of organic contaminants

Pollution of water bodies is one of the most common environmental problems today. Organic pollutants are one of the main drawbacks in this natural resource, among which the following stand out long-lived dyes, pharmaceuticals, and pesticides. This research aims at obtaining nanocomposites based on polycaprolactone-chitosan (PCL-CS) electrospun nanofibers (NFs) containing TiO2 nanoparticles (NPs) for the adsorption and photocatalytic degradation of organic pollutants, using Rhodamine B as a model. The fabricated hybrid materials were characterized by FT-IR, TGA, DSC, SEM, TEM, tensile properties, and the contact angle of water drops. The photoactivity of the NFs was investigated using a batch-type system by following UV-Vis absorbance and fluorescence of rhodamine B (RhB). For this purpose, TiO2NPs were successfully ex-situ incorporated into the polymer matrix promoting good mechanical properties and higher hydrophilicity of the material. The results showed that CS in the NFs increased the absorption and degradation of RhB by the TiO2NPs. CS attracted the pollutant molecules to the active sites vicinity of TiO2NPs, favoring initial adsorption and degradation. In other words, a bait-hook-and-destroy effect was evidenced. It also was demonstrated that the sensitization of TiO2 by organic dyes (e.g., perylene derivative) considerably improves the photocatalytic activity under visible radiation, allowing the use of low amounts of TiO2. (≈0.05 g/1 g of fiber). Hence, the current study is expected to contribute with an environmentally friendly green alternative solution.