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.

Arte e commercio dell'arte. Le origini delle collezioni della cassa di risparmio in Bologna e il fondo di incisioni carraccesche della raccolta Casati

La ricerca ha mirato a ricostruire storicamente quali furono le motivazioni che, tra la fine del XIX e gli inizi del XX secolo, portarono gli amministratori della Cassa Risparmio in Bologna a progettare la creazione di un Museo d’arte e di Storia della città, delineandone quelli che furono i principali responsabili e protagonisti. Dall’analisi dei documenti conservati presso l’Archivio della Cassa di Risparmio è emerso uno studio approfondito dei protagonisti della politica artistica e culturale dell’Istituto, oltre che dei legami e delle relazioni intessute con le principali istituzioni cittadine. Lo studio si è progressivamente focalizzato su un particolare momento della storia di Bologna, quando, in seguito all’approvazione del Piano Regolatore del 1889, la città fu per oltre un trentennio sottoposta a radicali trasformazioni urbanistiche che ne cambiarono completamente l’aspetto. Tra i personaggi finora ignoti di questa storia è emerso il nome dell’ingegnere Giambattista Comelli, consigliere e vice segretario della banca alla fine del XIX secolo, che per primo, nel 1896, avanzò la proposta di creare un museo dell’Istituto. A differenza di quanto ritenuto sino ad oggi, questo avrebbe dovuto avere, nelle intenzioni originarie, esclusivamente funzione di riunire e mostrare oggetti e documenti inerenti la nascita e lo sviluppo della Cassa di Risparmio. Un museo, dunque, che ne celebrasse l’attività, mostrando alla città come la banca avesse saputo rispondere prontamente e efficacemente, anche nei momenti più critici, alle esigenze dei bolognesi. Personaggio oggi dimenticato, Comelli fu in realtà figura piuttosto nota in ambito cittadino, inserita nei principali sodalizi culturali dell’epoca, tra cui la Regia Deputazione di Storia Patria e il Comitato per Bologna Storico Artistica, assieme a quei Rubbiani, Cavazza e Zucchini, che tanta influenza ebbero, come vedremo in seguito, sugli orientamenti Si dovettero tuttavia aspettare almeno due decenni, affinché l’idea originaria di fondare un Museo della Cassa di Risparmio si evolvesse in un senso più complesso e programmatico. Le ricerche hanno infatti evidenziato che le Raccolte d’Arte della Cassa di Risparmio non avrebbero acquistato l’importanza e la consistenza che oggi ci è dato constatare senza l’intervento decisivo di un personaggio noto fino ad oggi soltanto per i suoi indubbi meriti artistici: Alfredo Baruffi. Impiegato come ragioniere della Cassa fin dai diciotto anni, il Baruffi divenne, una volta pensionato, il “conservatore” delle Collezioni della Cassa di Risparmio. Fu lui a imprimere un nuovo corso all’originaria idea di Comelli, investendo tutte le proprie energie nella raccolta di dipinti, disegni, incisioni, libri, incunaboli, autografi, fotografie e oggetti d’uso quotidiano, col proposito di creare un museo che raccontasse la storia di Bologna e delle sue ultime grandi trasformazioni urbanistiche. Attraverso l’attenta analisi dei documenti cartacei e il raffronto con le opere in collezione è stato quindi possibile ricostruire passo dopo passo la nascita di un progetto culturale di ampia portata. La formazione della raccolta fu fortemente influenzata dalle teorie neomedievaliste di Alfonso Rubbiani, oltre che dalla volontà di salvaguardare, almeno a livello documentario, la memoria storica della Bologna medievale che in quegli anni stava per essere irrimediabilmente cancellata. Le scelte che orientarono la raccolta dei materiali, recentemente confluiti per la maggior parte nelle Collezioni della Fondazione della Cassa di Risparmio in Bologna, acquistano, con questo studio una nuova valenza grazie alla scoperta degli stretti rapporti che Baruffi intrattenne coi principali rappresentanti della cerchia rubbianesca, tra cui Francesco Cavazza, Guido Zucchini e Albano Sorbelli. Con essi Baruffi partecipò infatti a numerosi sodalizi e iniziative quali il Comitato per Bologna Storico Artistica, la “Mostra Bologna che fu” e la società Francesco Francia, che segnarono profondamente l’ambiente culturale cittadino. La portata e la qualità delle scelte condotte da Baruffi nell’acquisto e raccolta dei materiali si rivela ancora oggi, a distanza di quasi un secolo, attenta e mirata per il ruolo documentario che le Raccolte avevano e hanno assunto quali preziose e spesso uniche testimonianze del recente passato cittadino. Esaminata tutta la documentazione inerente la nascita delle Raccolte, la ricerca si è ha successivamente concentrata sulla vicenda di acquisto del fondo delle incisioni carraccesche della collezione Casati. La prima parte del lavoro è consistita nel repertoriare e trascrivere tutti i documenti relativi alla transazione d’acquisto, avvenuta nel 1937, vicenda che per la sua complessità impegnò per molti mesi, in un fitto carteggio, Baruffi, la direzione della Cassa e l’antiquario milanese Cesare Fasella. Il raffronto tra documenti d’archivio, inventari e materiale grafico ha permesso di ricostituire, seppur con qualche margine di incertezza, l’intera collezione Casati, individuando quasi 700 incisioni e 22 dei 23 disegni che la componevano. L’ultima fase di studio ha visto l’inventariazione e la catalogazione delle 700 incisioni. Il catalogo è stato suddiviso per autori, partendo dalle incisioni attribuite con certezza ad Agostino e ai suoi copisti, per poi passare ad Annibale e a Ludovico e ai loro copisti. Le incisioni studiate si sono rivelate tutte di grande qualità. Alcuni esemplari sono inoltre particolarmente significativi dal punto di vista storico-critico, perché mai citati nei tre principali e più recenti repertori di stampe carraccesche. Lo studio si conclude con l’individuazione di una stretta correlazione tra il pensiero e della pratica operatività in qualità di archivista, museografo e opinionista, di un altrettanto decisivo protagonista della ricerca, lo storico dell’arte Corrado Ricci, la cui influenza esercitata nell’ambiente culturale bolognese di quegli anni è già sottolineata nel primo capitolo. La conclusione approfondisce i possibili raporti e legami tra Baruffi e Corrado Ricci i cui interventi attorno alla questione della tutela e della salvaguardia del patrimonio storico, artistico, e paesaggistico italiano furono fondamentali per la nascita di una coscienza artistica e ambientale comune e per il conseguente sviluppo di leggi ad hoc. Numerose furono infatti le occasioni d’incontro tra Baruffi e Ricci. Qesti fu socio onorario del Comitato per Bologna Storico Artistica, nonché, quando era già Direttore Generale delle Belle Arti, presidente della storica mostra “Bologna che fu”. Sia Ricci che Baruffi fecero inoltre parte di quelle iniziative volte alla difesa e alla valorizzazione del paesaggio naturale, inteso anche in un ottica di promozione turistica, che videro la nascita proprio in Emilia Romagna: nel 1889 nasce l’Associazione Pro Montibus et silvis, del 1906 è l’Associazione nazionale per i paesaggi e monumenti pittoreschi, del 1912 è la Lega Nazionale per la protezione dei monumenti naturali. Queste iniziative si concretizzarono con la fondazione a Milano nel 1913 del Comitato Nazionale per la difesa del paesaggio e i monumenti italici, costituitosi presso la sede del Touring Club Italiano. Quelle occasioni d’incontro, come pure gli scritti di Ricci, trovarono certamente un terreno fertile in Baruffi conservatore, che nella formazione delle Collezioni, come pure nelle sua attività di “promotore culturale”, ci appare oggi guidato dalle teorie e dall’esempio pratico dei due numi tutelari: Alfonso Rubbiani e Corrado Ricci. La ricerca di documentazione all’interno di archivi e biblioteche cittadine, ha infine rivelato che il ruolo svolto da Baruffi come “operatore culturale” non fu quello di semplice sodale, ma di vero protagonista della scena bolognese. Soprattutto a partire dal secondo decennio del Novecento, quando fors’anche a seguito della morte del “maestro” Rubbiani, egli divenne uno tra i personaggi più impegnati in iniziative di tutela e promozione del patrimonio artistico cittadino, antico e moderno che fosse, intese a condizionare la progettualità politica e culturale della città. In tale contesto si può ben arguire il ruolo che avrebbero assunto le Collezioni storico artistiche numismatiche, popolaresche, della Cassa di Risparmio, cui Baruffi dedicò tutta la sua carriera successiva.

El Niño southern oscillation and its effect on fog oases along the Peruvian and Chilean coastal deserts

Fog oases, locally named Lomas, are distributed in a fragmented way along the western coast of Chile and Peru (South America) between ~6°S and 30°S following an altitudinal gradient determined by a fog layer. This fragmentation has been attributed to the hyper aridity of the desert. However, periodically climatic events influence the ‘normal seasonality’ of this ecosystem through a higher than average water input that triggers plant responses (e.g. primary productivity and phenology). The impact of the climatic oscillation may vary according to the season (wet/dry). This thesis evaluates the potential effect of climate oscillations, such as El Niño Southern Oscillation (ENSO), through the analysis of vegetation of this ecosystem following different approaches: Chapters two and three show the analysis of fog oasis along the Peruvian and Chilean deserts. The objectives are: 1) to explain the floristic connection of fog oases analysing their taxa composition differences and the phylogenetic affinities among them, 2) to explore the climate variables related to ENSO which likely affect fog production, and the responses of Lomas vegetation (composition, productivity, distribution) to climate patterns during ENSO events. Chapters four and five describe a fog-oasis in southern Peru during the 2008-2010 period. The objectives are: 3) to describe and create a new vegetation map of the Lomas vegetation using remote sensing analysis supported by field survey data, and 4) to identify the vegetation change during the dry season. The first part of our results show that: 1) there are three significantly different groups of Lomas (Northern Peru, Southern Peru, and Chile) with a significant phylogenetic divergence among them. The species composition reveals a latitudinal gradient of plant assemblages. The species origin, growth-forms typologies, and geographic position also reinforce the differences among groups. 2) Contradictory results have emerged from studies of low-cloud anomalies and the fog-collection during El Niño (EN). EN increases water availability in fog oases when fog should be less frequent due to the reduction of low-clouds amount and stratocumulus. Because a minor role of fog during EN is expected, it is likely that measurements of fog-water collection during EN are considering drizzle and fog at the same time. Although recent studies on fog oases have shown some relationship with the ENSO, responses of vegetation have been largely based on descriptive data, the absence of large temporal records limit the establishment of a direct relationship with climatic oscillations. The second part of the results show that: 3) five different classes of different spectral values correspond to the main land cover of Lomas using a Vegetation Index (VI). The study case is characterised by shrubs and trees with variable cover (dense, semi-dense and open). A secondary area is covered by small shrubs where the dominant tree species is not present. The cacti area and the old terraces with open vegetation were not identified with the VI. Agriculture is present in the area. Finally, 4) contrary to the dry season of 2008 and 2009 years, a higher VI was obtained during the dry season of 2010. The VI increased up to three times their average value, showing a clear spectral signal change, which coincided with the ENSO event of that period.

Development of oil spill detection techniques for satellite optical sensors and their application to monitor oil spill discharge in Mediterranean sea

Satellite remote sensing has proved to be an effective support in timely detection and monitoring of marine oil pollution, mainly due to illegal ship discharges. In this context, we have developed a new methodology and technique for optical oil spill detection, which make use of MODIS L2 and MERIS L1B satellite top of atmosphere (TOA) reflectance imagery, for the first time in a highly automated way. The main idea was combining wide swaths and short revisit times of optical sensors with SAR observations, generally used in oil spill monitoring. This arises from the necessity to overcome the SAR reduced coverage and long revisit time of the monitoring area. This can be done now, given the MODIS and MERIS higher spatial resolution with respect to older sensors (250-300 m vs. 1 km), which consents the identification of smaller spills deriving from illicit discharge at sea. The procedure to obtain identifiable spills in optical reflectance images involves removal of oceanic and atmospheric natural variability, in order to enhance oil-water contrast; image clustering, which purpose is to segment the oil spill eventually presents in the image; finally, the application of a set of criteria for the elimination of those features which look like spills (look-alikes). The final result is a classification of oil spill candidate regions by means of a score based on the above criteria.

Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.

Pharmaceutical residues in aquatic systems: mode of action and effects on mussel physiology

Pharmaceutical residues contaminate aquatic ecosystems as a result of their widespread human and veterinary usage. Since continuously released and not efficiently removed, certain pharmaceuticals exhibit pseudo-persistence thus generating concerns for the health of aquatic wildlife. This work aimed at assessing on mussels Mytilus galloprovincialis, under laboratory conditions, the effects of three pharmaceuticals, carbamazepine (antiepileptic), propranolol (β-blocker) and oxytetracycline (antibiotic), to evaluate if the human-based mode of action of these molecules is conserved in invertebrates. Furthermore, in the framework of the European MEECE Programme, mussels were exposed to oxytetracycline and copper at increasing temperatures, simulating variations due to climate changes. The effects of these compounds were assessed evaluating a battery of biomarkers, the expression of HSP70 proteins and changes in cAMP-related parameters. A decrease in lysosomal membrane stability, induction of oxidative stress, alterations of cAMP-dependent pathway and the induction of defense mechanisms were observed indicating the development of a stress syndrome, and a worsening in mussels health status. Data obtained in MEECE Programme confirmed that the toxicity of substances can be enhanced following changes in temperature. The alterations observed were obtained after exposure to pharmaceuticals at concentrations sometimes lower than those detected in the aquatic environment. Hence, further research is advisable regarding subtle effects of pharmaceuticals on non-target organisms. Furthermore, results obtained during a research stay in the laboratories of Cádiz University (Spain) are presented. The project aimed at measuring possible effects of polluted sediments in Algeciras Bay (Spain) and in Cádiz Bay, by assessing different physiological parameters in caged crabs Carcinus maenas and clams Ruditapes decussatus exposed in situ for 28 days. The neutral red retention assay was adapted to these species and proved to be a sensitive screening tool for the assessment of sediment quality.

Harmful algae and their potential impacts on the coastal ecosystem: growth and toxin production dynamics

The main goal of the present thesis was to study some harmful algal species which cause blooms in Italian coastal waters, leading to consequences for human health, coastal ecosystem, fishery and tourism. In particular, in the first part of this thesis the toxicity of Adriatic strains of the raphidophyte Fibrocapsa japonica was investigated. Despite several hypotheses have been proposed for the toxic mechanism of the raphidophytes, especially for the species Chattonella antiqua and C. marina, which have been studied more extensively, just a few studies on the toxic effects of these species for different organisms were reported. Moreover, a careful reading of the literature evidenced as any ichthyotoxic events reported worldwide can be linked to F. japonica blooms. Although recently several studies were performed on F. japonica strains from the USA, Japan, Australia, New Zealand, the Netherlands, Germany, and France in order to characterize their growth and toxicity features, the work reported in this thesis results one of the first investigation on the toxic effects of F. japonica for different organisms, such as bacteria, crustaceans and fish. Mortality effects, together with haemolysis of fish erythrocytes, probably due to the relatively high amount of PUFAs produced by this species, were observed. Mortality for fish, however, was reported only at a high cell density and after a long exposition period (9-10 days); moreover a significant increase of H2O2 obtained in the tanks where sea basses were exposed to F. japonica was also relevant. This result may justify the absence of ichthyotoxic events in the Italian coasts, despite F. japonica blooms detected in these areas were characterized by high cell densities. This work reports also a first complete characterization of the fatty acids produced and extracellularly released by the Adriatic F. japonica, and results were also compared with the fatty acid profile of other strains. The absence of known brevetoxins in F. japonica algal extracts was also highlighted, leading to the hypothesis that the toxicity of F. japonica may be due to a synergic effect of PUFAs and ROS. Another microalgae that was studied in this thesis is the benthic dinoflagellate Ostreopsis cf. ovata. This species was investigated with the aim to investigate the effect of environmental parameters on its growth and toxicity. O. cf. ovata, in fact, shows different blooming periods along the Italian coasts and even the reported toxic effects are variable. The results of this work confirmed the high variability in the growth dynamic and toxin content of several Italian strains which were isolated in recent years along the Adriatic and Tyrrhenian Seas. Moreover, the effects of temperature and salinity on the behaviour of the different isolates are in good agreement with the results obtained from field surveys, which evidence as the environmental parameters are important factors modulating O. cf. ovata proliferation. Another relevant result that was highlighted is the anomaly in the production of palytoxin-like compounds reported by one of the studied isolate, in particular the one isolated in 2008 in Ancona (Adriatic Sea). Only this strain reported the absence of two (ovatoxin-b and –c) of the five ovatoxins so far known in the toxin profile and a different relative abundance of the other toxins. The last aspect that was studied in this thesis regards the toxin biosythesis. In fact, toxins produced (palytoxin-like compounds) or supposed to be produced (brevetoxin-like compounds) by O. cf. ovata and F. japonica, respectively, are polyketides, which are highly oxygenated compounds synthesized by complex enzymes known as polyketide synthase (PKS) enzymes. These enzymes are multi-domain complexes that structurally and functionally resemble the fatty acid synthases (FASs). This work reports the first study of PKS proteins in the dinoflagellates O. cf. ovata, C. monotis and in the raphidophyte F. japonica. For the first time some PKSs were identified in these species, confirming the presence of PKS proteins predicted by the in silico translation of the transcripts found in K. brevis also in other species. The identification of O. cf. ovata PKSs and the localization of the palytoxin-like compounds produced by this dinoflagellate in a similar location (chloroplast) as that observed for other dinoflagellate and cyanobacterial toxins provides some indication that these proteins may be involved in polyketide biosynthesis. However, their potential function as fatty acid synthases cannot be ruled out, as plant fatty acid synthesis also occurs within chloroplasts. This last hypothesis is also supported by the fact that in all the investigated species, and in particular in F. japonica, PKS proteins were present. Therefore, these results provide an important contribution to the study of the polyketides and of the involvement of PKS proteins in the toxin biosynthesis.

Spatial and temporal variability and ecological processes in the epibenthic assemblages of the northern Adriatic Sea

Several coralligenous reefs occur in the soft bottoms of the northern Adriatic continental shelf. Mediterranean coralligenous habitats are characterised by high species diversity and are intrinsically valuable for their biological diversity and for the ecological processes they support. The conservation and management of these habitats require quantifying spatial and temporal variability of their benthic assemblages. This PhD thesis aims to give a relevant contribution to the knowledge of the structure and dynamics of the epibenthic assemblages on the coralligenous subtidal reefs occurring in the northern Adriatic Sea. The epibenthic assemblages showed a spatial variation larger compared to temporal changes, with a temporal persistence of reef-forming organisms. Assemblages spatial heterogeneity has been related to morphological features and geographical location of the reefs, together with variation in the hydrological conditions. Manipulative experiments help to understand the ecological processes structuring the benthic assemblages and maintaining their diversity. In this regards a short and long term experiment on colonization patterns of artificial substrata over a 3-year period has been performed in three reefs, corresponding to the three main types of assemblages detected in the previous study. The first colonisers, largely depending by the different larval supply, played a key role in determining the heterogeneity of the assemblages in the early stage of colonisation. Lateral invasion, from the surrounding assemblages, was the driver in structuring the mature assemblages. These complex colonisation dynamics explained the high heterogeneity of the assemblages dwelling on the northern Adriatic biogenic reefs. The buildup of these coralligenous reefs mainly depends by the bioconstruction-erosion processes that has been analysed through a field experiment. Bioconstruction, largely due to serpulid polychaetes, prevailed on erosion processes and occurred at similar rates in all sites. Similarly, the total energy contents in the benthic communities do not differ among sites, despite being provided by different species. Therefore, we can hypothesise that both bioconstruction processes and energetic storage may be limited by the availability of resources. Finally the major contribution of the zoobenthos compared to the phytobenthos to the total energetic content of assemblages suggests that the energy flow in these benthic habitats is primarily supported by planktonic food web trough the filter feeding invertebrates.

Sustainability indicators for environmental management and decision making

The general objective of this research is to explore theories and methodologies of sustainability indicators, environmental management and decision making disciplines with the operational purpose of producing scientific, robust and relevant information for supporting system understanding and decision making in real case studies. Several tools have been applied in order to increase the understanding of socio-ecological systems as well as providing relevant information on the choice between alternatives. These tools have always been applied having in mind the complexity of the issues and the uncertainty tied to the partial knowledge of the systems under study. Two case studies with specific application to performances measurement (environmental performances in the case of the K8 approach and sustainable development performances in the case of the EU Sustainable Development Strategy) and a case study about the selection of sustainable development indicators amongst Municipalities in Scotland, are discussed in the first part of the work. In the second part of the work, the common denominator among subjects consists in the application of spatial indices and indicators to address operational problems in land use management within the territory of the Ravenna province (Italy). The main conclusion of the thesis is that a ‘perfect’ methodological approach which always produces the best results in assessing sustainability performances does not exist. Rather, there is a pool of correct approaches answering different evaluation questions, to be used when methodologies fit the purpose of the analysis. For this reason, methodological limits and conceptual assumptions as well as consistency and transparency of the assessment, become the key factors for assessing the quality of the analysis.

Development of Organocatalytic stereoselective SN1 type reactions

The proposal in my thesis has been the study of Stereoselective α-alkylation through SN1 type reaction. SN1 type reaction involves a stabilized and reactive carbocation intermediate By taking advantages of stability of particular carbocations, the use of carbocations in selective reactions has been important. In this work has been necessary to know the stability and reactivity of carbocations. And the work of Mayr group has helped to rationalize the behaviour and reactivity between the carbocations and nucleophiles by the use of Mayr’s scale of reactivity. The use of alcohols to performed the stable and reactive carbocations have been the key in my thesis. The direct nucleophilic substitution of alcohols has been a crucial scope in the field of organic synthesis, because offer a wide range of intermediates for the synthesis of natural products and pharmaceutics synthesis. In particular the catalytic nucleophilic direct substitution of alcohols represents a novel methodology for the preparation of a variety of derivatives, and water only as the sub-product in the reaction. The stereochemical control of the transformation C-H bond into stereogenic C-C bond adjacent to carbonyl functionalized has been studied for asymmetric catalysis. And the field of organocatalysis has introduced the use of small organic molecule as catalyst for stereoselective transformations. Merging these two concepts Organocatalysis and Mayr’s scale, my thesis has developed a new approach for the α-alkylation of aldehydes and ketones through SN1 type reaction.

Conservazione del seme sortato di suino

Gli spermatozoi di suino sottoposti alla procedura di sessaggio mediante citofluorimetria presentano una serie di modificazioni morfo-funzionali che compromettono nel tempo la loro sopravvivenza e la capacità fecondante. Questi spermatozoi, inoltre, a causa della sensibilità ai danni indotti dalla crioconservazione, vengono solitamente conservati allo stato liquido a 15-17°C, con conseguente ulteriore peggioramento nel tempo della qualità delle cellule spermatiche sessate. Lo scopo della ricerca è stato quello di valutare le modificazioni di alcune caratteristiche morfo-funzionali degli spermatozoi in seguito a sex-sorting e conseguente conservazione. Successivamente si è cercato di migliorare i parametri qualitativi del seme sessato mediante l’aggiunta di sostanze antiossidanti e la messa a punto di una nuova metodica di conservazione. I risultati ottenuti hanno evidenziato che la procedura di sessaggio e la conseguente conservazione per 24-26 ore a 15°C hanno indotto un peggioramento significativo delle caratteristiche morfo-funzionali (vitalità, integrità acrosomiale, quantità e distribuzione dell’Hsp70, capacità fecondante). Mentre l’azione degli antiossidanti non si è rivelata efficace nel miglioramento della qualità degli spermatozoi durante le fasi di colorazione e passaggio attraverso il citofluorimetro, l’azione congiunta del plasma seminale e degli antiossidanti superossido-dismutasi ed epigallocatechina-3-gallato ha indotto un miglioramento significativo della vitalità degli spermatozoi. Per la conservazione del seme di suino è stata testata la tecnica di incapsulazione in membrane di alginato di bario che permette, durante l’inseminazione artificiale, un rilascio graduale degli spermatozoi e l’utilizzo di un quantitativo inferiore di materiale seminale. L’applicazione di tale tecnica per la conservazione degli spermatozoi di suino sessati non sembra provocare un calo significativo della vitalità, dell’integrità acrosomiale e dell’efficienza totale di fecondazione rispetto al seme sortato e conservato diluito suggerendo futuri studi in vivo. Una migliore conoscenza dei danni indotti da queste tecnologie e la loro minimizzazione potrà stimolare in futuro l’utilizzo su vasta scala del seme sessato nel suino.

Algal wastewater treatment and biomass producing potential: nutrient removal efficiency and cell physiological responses

Microalgae are sun - light cell factories that convert carbon dioxide to biofuels, foods, feeds, and other bioproducts. The concept of microalgae cultivation as an integrated system in wastewater treatment has optimized the potential of the microalgae - based biofuel production. These microorganisms contains lipids, polysaccharides, proteins, pigments and other cell compounds, and their biomass can provide different kinds of biofuels such as biodiesel, biomethane and ethanol. The algal biomass application strongly depends on the cell composition and the production of biofuels appears to be economically convenient only in conjunction with wastewater treatment. The aim of this research thesis was to investigate a biological wastewater system on a laboratory scale growing a newly isolated freshwater microalgae, Desmodesmus communis, in effluents generated by a local wastewater reclamation facility in Cesena (Emilia Romagna, Italy) in batch and semi - continuous cultures. This work showed the potential utilization of this microorganism in an algae - based wastewater treatment; Desmodesmus communis had a great capacity to grow in the wastewater, competing with other microorganisms naturally present and adapting to various environmental conditions such as different irradiance levels and nutrient concentrations. The nutrient removal efficiency was characterized at different hydraulic retention times as well as the algal growth rate and biomass composition in terms of proteins, polysaccharides, total lipids and total fatty acids (TFAs) which are considered the substrate for biodiesel production. The biochemical analyses were coupled with the biomass elemental analysis which specified the amount of carbon and nitrogen in the algal biomass. Furthermore photosynthetic investigations were carried out to better correlate the environmental conditions with the physiology responses of the cells and consequently get more information to optimize the growth rate and the increase of TFAs and C/N ratio, cellular compounds and biomass parameter which are fundamental in the biomass energy recovery.

Sea-Level climate variability in the Mediterranean Sea

Sea-level variability is characterized by multiple interacting factors described in the Fourth Assessment Report (Bindoff et al., 2007) of the Intergovernmental Panel on Climate Change (IPCC) that act over wide spectra of temporal and spatial scales. In Church et al. (2010) sea-level variability and changes are defined as manifestations of climate variability and change. The European Environmental Agency (EEA) defines sea level as one of most important indicators for monitoring climate change, as it integrates the response of different components of the Earths system and is also affected by anthropogenic contributions (EEA, 2011). The balance between the different sea-level contributions represents an important source of uncertainty, involving stochastic processes that are very difficult to describe and understand in detail, to the point that they are defined as an enigma in Munk (2002). Sea-level rate estimates are affected by all these uncertainties, in particular if we look at possible responses to sea-level contributions to future climate. At the regional scale, lateral fluxes also contribute to sea-level variability, adding complexity to sea-level dynamics. The research strategy adopted in this work to approach such an interesting and challenging topic has been to develop an objective methodology to study sea-level variability at different temporal and spatial scales, applicable in each part of the Mediterranean basin in particular, and in the global ocean in general, using all the best calibrated sources of data (for the Mediterranean): in-situ, remote-sensig and numerical models data. The global objective of this work was to achieve a deep understanding of all of the components of the sea-level signal contributing to sea-level variability, tendency and trend and to quantify them.