Food Safety and Mineral Oil Contaminated Paperboard Packaging: an Analytical Challenge and a Migration Study

Food packaging protects food, but it can sometimes become a source of undesired contaminants. Paper based materials, despite being perceived as “natural” and safe, can contain volatile contaminants (especially if made from recycled paper) able to migrate to food, as mineral oil, phthalates and photoinitiators. Mineral oil is a petroleum product used as printing ink solvent for newspapers, magazines and packaging. From paperboard printing and from recycled fibers (if present), mineral oil migrates into food, even if dry, through the gas phase. Its toxicity is not fully evaluated, but a temporary Acceptable Daily Intake (ADI) of 0.6 mg kg-1 has been established for saturated mineral oil hydrocarbons (MOSH), while aromatic hydrocarbons (MOAH) are more toxic. Extraction and analysis of MOSH and MOAH is difficult due to the thousands of molecules present. Extraction methods for packaging and food have been optimized, then applied for a “shopping trolley survey” on over 100 Italian and Swiss market products. Instrumental analyses were performed with online LC-GC/FID. Average concentration of MOSH in paperboards was 626 mg kg-1. Many had the potential of contaminating foods exceeding temporary ADI tens of times. A long term migration study was then designed to better understand migration kinetics. Egg pasta and müesli were chosen as representative (high surface/weight ratio). They were stored at different temperatures (4, 20, 30, 40 and 60°C) and conditions (free, shelved or boxed packs) for 1 year. MOSH and MOAH kinetic curves show that migration is a fast process, mostly influenced by temperature: in egg pasta (food in direct contact with paperboard), half of MOSH is transferred to food in a week at 40°C and in 8 months at 20°C. The internal plastic bag present in müesli slowed down the startup of migration, creating a “lag time” in the curves.

Technological processes study for high value health ingredients and foods production

This PhD thesis describes set up of technological models for obtaining high health value foods and ingredients that preserve the final product characteristics as well as enrich with nutritional components. In particular, the main object of my research has been Virgin Olive Oil (VOO) and its important antioxidant compounds which differentiate it from all other vegetables oils. It is well known how the qualitative and quantitative presence of phenolic molecules extracted from olives during oil production is fundamental for its oxidative and nutritional quality. For this purpose, agronomic and technological conditions of its production have been investigated. It has also been examined how this fraction can be better preserved during storage. Moreover, its relation with VOO sensorial characteristics and its interaction with a protein in emulsion foods have also been studied. Finally, an experimental work was carried out to determine the antioxidative and heat resistance properties of a new antioxidant (EVS-OL) when used for high temperature frying such as is typically employed for the preparation of french fries. Results of the scientific research have been submitted for a publication and some data has already been published in national and international scientific journals.

Strategies and procedures for the development of intermodal freight transport in Europe: the role of motorways of the sea services and railway terminals

Since the birth of the European Union on 1957, the development of a single market through the integration of national freight transport networks has been one of the most important points in the European Union agenda. Increasingly congested motorways, rising oil prices and concerns about environment and climate change require the optimization of transport systems and transport processes. The best solution should be the intermodal transport, in which the most efficient transport options are used for the different legs of transport. This thesis examines the problem of defining innovative strategies and procedures for the sustainable development of intermodal freight transport in Europe. In particular, the role of maritime transport and railway transport in the intermodal chain are examined in depth, as these modes are recognized to be environmentally friendly and energy efficient. Maritime transport is the only mode that has kept pace with the fast growth in road transport, but it is necessary to promote the full exploitation of it by involving short sea shipping as an integrated service in the intermodal door-to-door supply chain and by improving port accessibility. The role of Motorways of the Sea services as part of the Trans-European Transport Network is is taken into account: a picture of the European policy and a state of the art of the Italian Motorways of the Sea system are reported. Afterwards, the focus shifts from line to node problems: the role of intermodal railway terminals in the transport chain is discussed. In particular, the last mile process is taken into account, as it is crucial in order to exploit the full capacity of an intermodal terminal. The difference between the present last mile planning models of Bologna Interporto and Verona Quadrante Europa is described and discussed. Finally, a new approach to railway intermodal terminal planning and management is introduced, by describing the case of "Terminal Gate" at Verona Quadrante Europa. Some proposals to favour the integrate management of "Terminal Gate" and the allocation of its capacity are drawn up.

Neutronics analyses for fast spectrum nuclear systems and scenario studies for advanced nuclear fuel cycles

The present PhD thesis summarizes the three-years study about the neutronic investigation of a new concept nuclear reactor aiming at the optimization and the sustainable management of nuclear fuel in a possible European scenario. A new generation nuclear reactor for the nuclear reinassance is indeed desired by the actual industrialized world, both for the solution of the energetic question arising from the continuously growing energy demand together with the corresponding reduction of oil availability, and the environment question for a sustainable energy source free from Long Lived Radioisotopes and therefore geological repositories. Among the Generation IV candidate typologies, the Lead Fast Reactor concept has been pursued, being the one top rated in sustainability. The European Lead-cooled SYstem (ELSY) has been at first investigated. The neutronic analysis of the ELSY core has been performed via deterministic analysis by means of the ERANOS code, in order to retrieve a stable configuration for the overall design of the reactor. Further analyses have been carried out by means of the Monte Carlo general purpose transport code MCNP, in order to check the former one and to define an exact model of the system. An innovative system of absorbers has been conceptualized and designed for both the reactivity compensation and regulation of the core due to cycle swing, as well as for safety in order to guarantee the cold shutdown of the system in case of accident. Aiming at the sustainability of nuclear energy, the steady-state nuclear equilibrium has been investigated and generalized into the definition of the ``extended'' equilibrium state. According to this, the Adiabatic Reactor Theory has been developed, together with a New Paradigm for Nuclear Power: in order to design a reactor that does not exchange with the environment anything valuable (thus the term ``adiabatic''), in the sense of both Plutonium and Minor Actinides, it is required indeed to revert the logical design scheme of nuclear cores, starting from the definition of the equilibrium composition of the fuel and submitting to the latter the whole core design. The New Paradigm has been applied then to the core design of an Adiabatic Lead Fast Reactor complying with the ELSY overall system layout. A complete core characterization has been done in order to asses criticality and power flattening; a preliminary evaluation of the main safety parameters has been also done to verify the viability of the system. Burn up calculations have been then performed in order to investigate the operating cycle for the Adiabatic Lead Fast Reactor; the fuel performances have been therefore extracted and inserted in a more general analysis for an European scenario. The present nuclear reactors fleet has been modeled and its evolution simulated by means of the COSI code in order to investigate the materials fluxes to be managed in the European region. Different plausible scenarios have been identified to forecast the evolution of the European nuclear energy production, including the one involving the introduction of Adiabatic Lead Fast Reactors, and compared to better analyze the advantages introduced by the adoption of new concept reactors. At last, since both ELSY and the ALFR represent new concept systems based upon innovative solutions, the neutronic design of a demonstrator reactor has been carried out: such a system is intended to prove the viability of technology to be implemented in the First-of-a-Kind industrial power plant, with the aim at attesting the general strategy to use, to the largest extent. It was chosen then to base the DEMO design upon a compromise between demonstration of developed technology and testing of emerging technology in order to significantly subserve the purpose of reducing uncertainties about construction and licensing, both validating ELSY/ALFR main features and performances, and to qualify numerical codes and tools.

Phytoplankton Response to Environmental Variables and Organic Pollutants. Laboratory Cultures and Numerical Simulations Experiments

Herbicides are becoming emergent contaminants in Italian surface, coastal and ground waters, due to their intensive use in agriculture. In marine environments herbicides have adverse effects on non-target organisms, as primary producers, resulting in oxygen depletion and decreased primary productivity. Alterations of species composition in algal communities can also occur due to the different sensitivity among the species. In the present thesis the effects of herbicides, widely used in the Northern Adriatic Sea, on different algal species were studied. The main goal of this work was to study the influence of temperature on algal growth in the presence of the triazinic herbicide terbuthylazine (TBA), and the cellular responses adopted to counteract the toxic effects of the pollutant (Chapter 1 and 2). The development of simulation models to be applied in environmental management are needed to organize and track information in a way that would not be possible otherwise and simulate an ecological prospective. The data collected from laboratory experiments were used to simulate algal responses to the TBA exposure at increasing temperature conditions (Chapter 3). Part of the thesis was conducted in foreign countries. The work presented in Chapter 4 was focused on the effect of high light on growth, toxicity and mixotrophy of the ichtyotoxic species Prymnesium parvum. In addition, a mesocosm experiment was conducted in order to study the synergic effect of the pollutant emamectin benzoate with other anthropogenic stressors, such as oil pollution and induced phytoplankton blooms (Chapter 5).

Identification and genetic diversity in phytoplasmas associated with diseases of cassava and other agronomic relevant crops in south-east Asia and Latin America

Identification and genetic diversity of phytoplasmas infecting tropical plant species, selected among those most agronomically relevant in South-east Asia and Latin America were studied. Correlation between evolutionary divergence of relevant phytoplasma strains and their geographic distribution by comparison on homologous genes of phytoplasma strains detected in the same or related plant species in other geographical areas worldwide was achieved. Molecular diversity was studied on genes coding ribosomal proteins, groEL, tuf and amp besides phytoplasma 16S rRNA. Selected samples infected by phytoplasmas belonging to diverse ribosomal groups were also studied by in silico RFLP followed by phylogenetic analyses. Moreover a partial genome annotation of a ‘Ca. P. brasiliense’ strain was done towards future application for epidemiological studies. Phytoplasma presence in cassava showing frog skin (CFSD) and witches’ broom (CWB) diseases in Costa Rica - Paraguay and in Vietnam – Thailand, respectively, was evaluated. In both cases, the diseases were associated with phytoplasmas related to aster yellows, apple proliferation and “stolbur” groups, while only phytoplasma related to X-disease group in CFSD, and to hibiscus witches’ broom, elm yellows and clover proliferation groups in CWB. Variability was found among strains belonging to the same ribosomal group but having different geographic origin and associated with different disease. Additionally, a dodder transmission assay to elucidate the role of phytoplasmas in CWB disease was carried out, and resulted in typical phytoplasma symptoms in periwinkle plants associated with the presence of aster yellows-related strains. Lethal wilt disease, a severe disease of oil palm in Colombia that is spreading throughout South America was also studied. Phytoplasmas were detected in symptomatic oil palm and identified as ‘Ca. P. asteris’, ribosomal subgroup 16SrI-B, and were distinguished from other aster yellows phytoplasmas used as reference strains; in particular, from an aster yellows strain infecting corn in the same country.

Quality control of virgin olive oils with regard to different storage and shipment conditions

Virgin olive oil(VOO) is a product characterized by high economic and nutritional values, because of its superior sensory characteristics and minor compounds (phenols and tocopherols) contents. Since the original quality of VOO may change during its storage, this study aimed to investigate the influence of different storage and shipment conditions on the quality of VOO, by studying different solutions such as filtration, dark storage and shipment inside insulated containers to protect it. Different analytical techniques were used to follow-up the quality changes during virgin olive oil storage and simulated shipments, in terms of basic quality parameters, sensory analysis and evaluation of minor components (phenolic compounds, diglycerides, volatile compounds). Four main research streams were presented in this PhD thesis: The results obtained from the first experimental section revealed that the application of filtration and/or clarification can decrease the unavoidable quality loss of the oil samples during storage, in comparison with unfiltered oil samples. The second section indicated that the virgin olive oil freshness, evaluated by diglycerides content, was mainly affected by the storage time and temperature. The third section revealed that fluctuation in temperature during storage may adversely affect the virgin olive oil quality, in terms of hydrolytic rancidity and oxidation quality. The fourth section showed that virgin olive oil shipped inside insulated containers showed lower hydrolytic and oxidation degradation than those without insulation cover. Overall, this PhD thesis highlighted that application of adequate treatment, such as filtration or clarification, in addition to a good protection against other external variables, such as temperature and light, will improve the stability of virgin olive oil during storage.