Analytical methods for evaluating the quality and the genuineness of olive oils

This Ph.D. thesis focuses on the investigation of some chemical and sensorial analytical parameters linked to the quality and purity of different categories of oils obtained by olives: extra virgin olive oils, both those that are sold in the large retail trade (supermarkets and discounts) and those directly collected at some Italian mills, and lower-quality oils (refined, lampante and “repaso”). Concurrently with the adoption of traditional and well-known analytical procedures such as gas chromatography and high-performance liquid chromatography, I carried out a set-up of innovative, fast and environmentally-friend methods. For example, I developed some analytical approaches based on Fourier transform medium infrared spectroscopy (FT-MIR) and time domain reflectometry (TDR), coupled with a robust chemometric elaboration of the results. I investigated some other freshness and quality markers that are not included in official parameters (in Italian and European regulations): the adoption of such a full chemical and sensorial analytical plan allowed me to obtain interesting information about the degree of quality of the EVOOs, mostly within the Italian market. Here the range of quality of EVOOs resulted very wide, in terms of sensory attributes, price classes and chemical parameters. Thanks to the collaboration with other Italian and foreign research groups, I carried out several applicative studies, especially focusing on the shelf-life of oils obtained by olives and on the effects of thermal stresses on the quality of the products. I also studied some innovative technological treatments, such as the clarification by using inert gases, as an alternative to the traditional filtration. Moreover, during a three-and-a-half months research stay at the University of Applied Sciences in Zurich, I also carried out a study related to the application of statistical methods for the elaboration of sensory results, obtained thanks to the official Swiss Panel and to some consumer tests.

In vitro application of biocontrol agents to improve the safety and quality of grapevine products

Pathogenic fungi are responsible for vine diseases affecting the grapevine yield and the organoleptic quality of the final wine products. Using of biocontrol agents can represent a sustainable alternative to the use of synthetic fungicides whose intense use can have negative effects on the ecosystem and cause increase resistant pathogen population to synthetic agents. The principal aim of my PhD thesis was the isolation and characterization of new yeast strains and Bacillus subtilis SV108 as biocontrol agent and the comprehension of the mechanism of their antimicrobial action. Accordingly, twenty wild yeast and one selected bacterium isolated among 62 samples, isolated from different Italian and Malaysian regions and molecularly identified, were evaluated in a preliminary screening test on agar. Results showed the highest effects on inhibiting mycelial growth by Starmerella bacillaris FE08.05, Metschnikowia pulcherrima GP8 and Hanseniaspora uvarum GM19. On the other side, Bacillus subtilis SV108 showed the ability of inhibit the mycelial growth of selected fungi by producing antimicrobial compounds on Malt Extract Broth medium recovered by sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) and identified by electrospray ionization (ESI) tandem mass spectrometer Triple TOF 5600. Moreover, in order to analyze the volatile fraction of compounds, the quantitative analysis of the VOCs profiles was performed by GC/MS/SPME. The analysis highlighted the presence of isoamyl and phenylethyl alcohols and an overall higher presence of low-chain fatty acids and volatile ethyl esters. All the data collected suggest that the tested yeasts, found among the epiphytic microbiota associated with grape berries, can be potentially effective for the biological control of pathogenic moulds. On the other hand, the proteomic study conducted on B. subtilis SV108 revealed that there are two cyclic antifungal peptides which can explain the antimicrobial effect of Bacillus subtilis SV108 acting as biocontrol agent against fungal pathogens in grapevine.

Reconciling the Irreconcilable? Sovereign Debt Restructuring and the Principles of International Law. A Law and Economics Perspective

This Thesis focuses on the principles of international law relevant to the resolution of legal disputes arising from sovereign insolvency conflicts. It attempts to contribute to the “incremental” approach literature by identifying principles, justifying their application in litigation and assessing whether they may help to reconcile the trade-offs prevalent in that context. For that purpose, this Thesis distinguishes between two different types of principles. First, it investigates the “Principles of Public International Law” (henceforth, “PIL principles”). Said category refers to norms of the law of nations which can be considered functionally and structurally similar to domestic constitutional principles (i.e., that can be regarded as “optimization” or “prima facie” requirements). This Thesis underscores the PIL principles protecting the interests of the creditors and citizens as well as the “public interest”, arguing that decision makers face a trade-off between these principles in the context of restructurings. Secondly, this Thesis inquires into the “general principles of domestic law” (henceforth, “GPDs”) which can be applied in sovereign debt restructuring. Two GPDs are identified: a “stay” on litigation and a “cram down” on dissenting creditors’ claims. Although both principles have been identified by the prior literature, this work advances a small but significant “twist” in the methodology used for that purpose: it relies exclusively on functional and comparative analysis. Moreover, this work justifies the application of said GPDs for two jurisdictions: New York and Germany. Finally, it posits that those GPDs can help to mitigate the trade-offs between PIL principles, thus reconciling the interests at stake.

Evaluation of the real nutritional value of processed food to improve their effect on health and increase their sustainability

Cured meats and dairy products are criticized for their salt content and synthetic additives. This has led to the development of strategies to reduce and replace these ingredients. Since the food matrix and technological processes can affect the bioaccessibility of nutrients, it is necessary to study their release during digestion to determine the real nutritional value of foods. In the first part of this PhD project, the impact on the nutritional quality of the reduction of sodium content and of the replacement of synthetic nitrates/nitrites with a combination of innovative formulations was evaluated in Parmigiano Reggiano Cheese and salami. For this purpose, an in vitro digestion model combined with different analytical techniques was used. The results showed that fatty acids and proteins release increased over time during digestion. At the end of digestion, the innovative formulation/processing did not negatively affect fatty acids release and protein hydrolysis, and led to the formation of bioactive peptides. The excessive intake of sugars is correlated with metabolic diseases. After the intestinal uptake, their release in the blood stream depends on their metabolic fate within the enterocyte. In the second part of this PhD project, the absorption and metabolism of glucose, fructose and sucrose was evaluated using intestinal cell line. A faster absorption of fructose than glucose was observed, and a different modulation of the synthesis/transport of other metabolites by monosaccharides was shown. Intestinal cells were also used to verify the stability and intestinal uptake of vitamins (A and D3) delivered to cells through two vehicles. It was shown that the presence of lipids protected the vitamin from external factors such as light, heat and oxygen, and improved their bioavailability Overall, the results obtained in this PhD project confirmed that considering only the chemical composition of foods is not sufficient to determine their nutritional value.

Toward an understanding of the atmospheric forcing uncertainties in the Mediterranean Sea

The thesis has extensively investigated for the first time the statistical distributions of atmospheric surface variables and heat fluxes for the Mediterranean Sea. After retrieving a 30-year atmospheric analysis dataset, we have captured the spatial patterns of the probability distribution of the relevant atmospheric variables for ocean atmospheric forcing: wind components (U,V), wind amplitude, air temperature (T2M), dewpoint temperature (D2M) and mean sea-level pressure (MSL-P). The study reveals that a two-parameter PDF is not a good fit for T2M, D2M, MSL-P and wind components (U,V) and a three parameter skew-normal PDF is better suited. Such distribution captures properly the data asymmetric tails (skewness). After removing the large seasonal cycle, we show the quality of the fit and the geographic structure of the PDF parameters. It is found that the PDF parameters vary between different regions, in particular the shape (connected to the asymmetric tails) and the scale (connected to the spread of the distribution) parameters cluster around two or more values, probably connected to the different dynamics that produces the surface atmospheric fields in the Mediterranean basin. Moreover, using the atmospheric variables, we have computed the air-sea heat fluxes for a 20-years period and estimated the net heat budget over the Mediterranean Sea. Interestingly, the higher resolution analysis dataset provides a negative heat budget of –3 W/m2 which is within the acceptable range for the Mediterranean Sea heat budget closure. The lower resolution atmospheric reanalysis dataset(ERA5) does not satisfy the heat budget closure problem pointing out that a minimal resolution of the atmospheric forcing is crucial for the Mediterranean Sea dynamics. The PDF framework developed in this thesis will be the basis for a future ensemble forecasting system that will use the statistical distributions to create perturbations of the atmospheric ocean forcing.