Metamorfismo ercinico di bassa-pressione: evoluzione tettonico-metamorfica del complesso di mandatoriccio (massiccio della Sila - Calabria)

Low-pressure/high-temperature (LP/HT) metamorphic belts are characterised by rocks that experienced abnormal heat flow in shallow crustal levels (T > 600 °C; P < 4 kbar) resulting in anomalous geothermal gradients (60-150 °C/km). The abnormal amount of heat has been related to crustal underplating of mantle-derived basic magmas or to thermal perturbation linked to intrusion of large volumes of granitoids in the intermediate crust. In particular, in this latter context, magmatic or aqueous fluids are able to transport relevant amounts of heat by advection, thus favouring regional LP/HT metamorphism. However, the thermal perturbation consequent to heat released by cooling magmas is responsible also for contact metamorphic effects. A first problem is that time and space relationships between regional LP/HT metamorphism and contact metamorphism are usually unclear. A second problem is related to the high temperature conditions reached at different crustal levels. These, in some cases, can completely erase the previous metamorphic history. Notwithstanding this problem is very marked in lower crustal levels, petrologic and geochronologic studies usually concentrate in these attractive portions of the crust. However, only in the intermediate/upper-crustal levels of a LP/HT metamorphic belt the tectono-metamorphic events preceding the temperature peak, usually not preserved in the lower crustal portions, can be readily unravelled. The Hercynian Orogen of Western Europe is a well-documented example of a continental collision zone with widespread LP/HT metamorphism, intense crustal anatexis and granite magmatism. Owing to the exposure of a nearly continuous cross-section of the Hercynian continental crust, the Sila massif (northern Calabria) represents a favourable area to understand large-scale relationships between granitoids and LP/HT metamorphic rocks, and to discriminate regional LP/HT metamorphic events from contact metamorphic effects. Granulite-facies rocks of the lower crust and greenschist- to amphibolite-facies rocks of the intermediate-upper crust are separated by granitoids emplaced into the intermediate level during the late stages of the Hercynian orogeny. Up to now, advanced petrologic studies have been focused mostly in understanding P-T evolution of deeper crustal levels and magmatic bodies, whereas the metamorphic history of the shallower crustal levels is poorly constrained. The Hercynian upper crust exposed in Sila has been subdivided in two different metamorphic complexes by previous authors: the low- to very low-grade Bocchigliero complex and the greenschist- to amphibolite-facies Mandatoriccio complex. The latter contains favourable mineral assemblages in order to unravel the tectono-metamorphic evolution of the Hercynian upper crust. The Mandatoriccio complex consists mainly of metapelites, meta-arenites, acid metavolcanites and metabasites with rare intercalations of marbles and orthogneisses. Siliciclastic metasediments show a static porphyroblastic growth mainly of biotite, garnet, andalusite, staurolite and muscovite, whereas cordierite and fibrolite are less common. U-Pb ages and internal features of zircons suggest that the protoliths of the Mandatoriccio complex formed in a sedimentary basin filled by Cambrian to Silurian magmatic products as well as by siliciclastic sediments derived from older igneous and metamorphic rocks. In some localities, metamorphic rocks are injected by numerous aplite/pegmatite veins. Small granite bodies are also present and are always associated to spotted schists with large porphyroblasts. They occur along a NW-SE trending transcurrent cataclastic fault zone, which represents the tectonic contact between the Bocchigliero and the Mandatoriccio complexes. This cataclastic fault zone shows evidence of activity at least from middle-Miocene to Recent, indicating that brittle deformation post-dated the Hercynian orogeny. P-T pseudosections show that micaschists and paragneisses of the Mandatoriccio complex followed a clockwise P-T path characterised by four main prograde phases: thickening, peak-pressure condition, decompression and peak-temperature condition. During the thickening phase, garnet blastesis started up with spessartine-rich syntectonic core developed within micaschists and paragneisses. Coevally (340 ± 9.6 Ma), mafic sills and dykes injected the upper crustal volcaniclastic sedimentary sequence of the Mandatoriccio complex. After reaching the peak-pressure condition (≈4 kbar), the upper crust experienced a period of deformation quiescence marked by the static overgrowths of S2 by Almandine-rich-garnet rims and by porphyroblasts of biotite and staurolite. Probably, this metamorphic phase is related to isotherms relaxation after the thickening episode recorder by the Rb/Sr isotopic system (326 ± 6 Ma isochron age). The post-collisional period was mainly characterised by decompression with increasing temperature. This stage is documented by the andalusite+biotite coronas overgrown on staurolite porphyroblasts and represents a critical point of the metamorphic history, since metamorphic rocks begin to record a significant thermal perturbation. Peak-temperature conditions (≈620 °C) were reached at the end of this stage. They are well constrained by some reaction textures and mineral assemblages observed almost exclusively within paragneisses. The later appearance of fibrolitic sillimanite documents a small excursion of the P-T path across the And-Sil boundary due to the heating. Stephanian U-Pb ages of monazite crystals from the paragneiss, can be related to this heating phase. Similar monazite U-Pb ages from the micaschist combined with the lack of fibrolitic sillimanite suggest that, during the same thermal perturbation, micaschists recorded temperatures slightly lower than those reached by paragneisses. The metamorphic history ended with the crystallisation of cordierite mainly at the expense of andalusite. Consequently, the Ms+Bt+St+And+Sill+Crd mineral assemblage observed in the paragneisses is the result of a polyphasic evolution and is characterised by the metastable persistence of the staurolite in the stability fields of the cordierite. Geologic, geochronologic and petrographic data suggest that the thermal peak recorded by the intermediate/upper crust could be strictly connected with the emplacement of large amounts of granitoid magmas in the middle crust. Probably, the lithospheric extension in the relatively heated crust favoured ascent and emplacement of granitoids and further exhumation of metamorphic rocks. After a comparison among the tectono-metamorphic evolutions of the different Hercynian crustal levels exposed in Sila, it is concluded that the intermediate/upper crustal level offers the possibility to reconstruct a more detailed tectono-metamorphic history. The P-T paths proposed for the lower crustal levels probably underestimate the amount of the decompression. Apart from these considerations, the comparative analysis indicates that P-T paths at various crustal levels in the Sila cross section are well compatible with a unique geologic scenario, characterized by post-collisional extensional tectonics and magmas ascent.

Advances in understanding of osmotic dehydration and vacuum impregnation of fruits

Osmotic Dehydration and Vacuum Impregnation are interesting operations in the food industry with applications in minimal fruit processing and/or freezing, allowing to develop new products with specific innovative characteristics. Osmotic dehydration is widely used for the partial removal of water from cellular tissue by immersion in hypertonic (osmotic) solution. The driving force for the diffusion of water from the tissue is provided by the differences in water chemical potential between the external solution and the internal liquid phase of the cells. Vacuum Impregnation of porous products immersed in a liquid phase consist of reduction of pressure in a solid-liquid system (vacuum step) followed by the restoration of atmospheric pressure (atmospheric step). During the vacuum step the internal gas in the product pores is expanded and partially flows out while during the atmospheric step, there is a compression of residual gas and the external liquid flows into the pores (Fito, 1994). This process is also a very useful unit operation in food engineering as it allows to introduce specific solutes in the tissue which can play different functions (antioxidants, pH regulators, preservatives, cryoprotectants etc.). The present study attempts to enhance our understanding and knowledge of fruit as living organism, interacting dynamically with the environment, and to explore metabolic, structural, physico-chemical changes during fruit processing. The use of innovative approaches and/or technologies such as SAFES (Systematic Approach to Food Engineering System), LF-NMR (Low Frequency Nuclear Magnetic Resonance), GASMAS (Gas in Scattering Media Absorption Spectroscopy) are very promising to deeply study these phenomena. SAFES methodology was applied in order to study irreversibility of the structural changes of kiwifruit during short time of osmotic treatment. The results showed that the deformed tissue can recover its initial state 300 min after osmotic dehydration at 25 °C. The LF-NMR resulted very useful in water status and compartmentalization study, permitting to separate observation of three different water population presented in vacuole, cytoplasm plus extracellular space and cell wall. GASMAS techniques was able to study the pressure equilibration after Vacuum Impregnation showing that after restoration of atmospheric pressure in the solid-liquid system, there was a reminding internal low pressure in the apple tissue that slowly increases until reaching the atmospheric pressure, in a time scale that depends on the vacuum applied during the vacuum step. The physiological response of apple tissue on Vacuum Impregnation process was studied indicating the possibility of vesicular transport within the cells. Finally, the possibility to extend the freezing tolerance of strawberry fruits impregnated with cryoprotectants was proven.

The role of the West African Monsoon in the tropical to mid-latitudes climate

The interaction between atmosphere–land–ocean–biosphere systems plays a prominent role on the atmospheric dynamics and on the convective rainfall distribution over the West Africa monsoon area during the boreal summer. In particular, the initialization of convective systems in the Sub – Sahelian region has been directly linked to soil moisture heterogeneities identified as the major triggering, development and propagation of convective systems. The present study aims at investigating African monsoon large scale convective dynamics and rainfall diurnal cycle through an exploration of the hypothesis behind the mechanisms of a monsoon phenomenon as an emergence of a collective dynamics of many propagating convective systems. Such hypothesis is based on the existence of an internal self – regulation mechanism among the various components. To achieve these results a multiple analysis was performed based on remote sensed rainfall dataset, and global and regional modelling data for a period of 5 seasons: 2004 - 2008. Satellite rainfall data and convective occurrence variability were studied for assessing typical spatio – temporal signatures and characteristics with an emphasis to the diurnal cycle footprint. A global model and regional model simulation datasets, specifically developed for this analysis and based on Regional Atmospheric Modelling System – RAMS, have been analysed. Results from numerical model datasets highlight the evidence of a synchronization between the destabilization of the convective boundary layer and rainfall occurrence due to the solar radiation forcing through the latent heat release. This supports the conclusion that the studied interacting systems are associated with a process of mutual adjustment of rhythms. Furthermore, this rainfall internal coherence was studied in relation to the West African Heat Low pressure system, which has a prominent role in the large scale summer variability over the Mediterranean area since it is acting as one of dynamic link between sub tropical and midlatitudes variability.

Design, synthesis and Chemical-physical characterization of photocatalytic inorganic nanocrystals for technological applications

This work was based on the synthesis and characterization of innovative crystals for biomedical and technological applications. Different types of syntheses were developed in order to obtain crystals with high photocatalytic properties. A hydrothermal synthesis was also processed to correlate the chemical-physical characteristics with synthesis parameters obtaining synthesis of nanoparticles of titanium dioxide with different morphology, size and crystalline phase depending on the variation of the synthesis parameters. Also a synthesis in water at 80 °C temperature and low pressure was developed from which anatase containing a small percentage of brookite nanoparticles were obtained, presenting a high photocatalytic activity. These particles have been used to obtain the microcrystals formed by an inorganic core of hydroxyapatite surface covered by TiO2 nanoparticles. Micrometer material with higher photocatalytic has been produced. The same nanoparticles have been functionalized with resorcinol oxidized in order to increase the photocatalytic efficiency. Photodegradation test results have confirmed this increase. Finally, synthetic nanoparticles with a waterless synthesis using formic acid and octanol, through esterification "in situ" were synthesized. Nanoparticles superficially covered by carboxylic residues able to bind a wide range of molecules to obtain further photocatalytic properties were obtained.

Innovative processes for syngas production

The research of new advanced processes for syngas production is a part of a European project for the production of a new Gas to Liquid Process (NextGTL). The crucial points in the production of GTL process are the energy required for the air separation used in autothermal reforming or the heat required for steam reforming and the efficiency in carbon utilization. Therefore a new multistep oxy-reforming process scheme was developed at lower temperature with intermediate H2 membrane separation to improve the crucial parameter. The process is characterized by a S/C of 0.7 and O2/C of 0.21 having a smoothed temperature profile in which kinetic regime is easily obtained. Active catalysts for low temperature oxy-reforming process have been studied working at low pressure to discriminate among the catalyst and at high pressure to prove it on industrial condition. It allows the selection of the Rh as active phase among single and bimetallic VIII group metal. The study of the matrix composition and thermal treatment has been carried out on Rh-Mg/Al hydrotalcite selected as reference catalyst. The research to optimize the catalyst lead to enhanced performances through the identification of a limitation of the Rh reduction from the oxides matrix as key point to increase the Rh performances. The Rh loading have been studied to allow the catalyst scale up for pilot process in Chieti in a shape of Rh-HT on honeycomb ceramic material. The developed catalyst has enhanced methane conversion in a inch diameter monolith reactor if compared with the semi-industrial catalyst chosen in the project as the best reference.

Studio del processo CVI/CVD per lo sviluppo di compositi ceramici rinforzati a fibra lunga

The most relevant thermo-mechanical properties of SiC or C based CFCCs are high strength, high toughness, low weight, high reliability, thermal shock and fatigue resistance. Thanks to these special characteristics, the CFCCs are the best candidates to substitute metals and monolithic ceramics, traditionally employed to realize components in energy, aeronautic and nuclear fields. Among the commonly techniques for the CFCCs production, CVI still represents the most significant one. Its main advantages are the versatility, the high quality deposits and the fact that it is conducted under mild temperature conditions. On the other hand, this technique is quite complex, therefore the set up of all process parameters needs long development time. The main purpose of the present study was to analyze the parameters controlling the CVD and CVI processes. Specifically, deposition and infiltration of SiC and Py-C tests were conducted on non-porous and porous substrates. The experiments were performed with a pilot size Isothermal/Isobaric CVI plant, designed and developed by ENEA. To guarantee the control of the process parameters, a previously optimization of the plant was needed. Changing temperature, pressure, flow rates and methane/hydrogen ratio, the Py-C deposition rate value, for an optimal fibre/matrix interphase thickness, was determined. It was also underlined the hydrogen inhibiting effect over the Py-C deposition rate. Regarding SiC morphologies, a difference between the inner and outer substrate surfaces was observed, as a consequence of a flow rate non-uniformity. In the case of the Cf/C composites development, the key parameter of the CVI process was the gas residence time. In fact, the hydrogen inhibiting effect was evident only with high value of residence time. Furthermore, lower the residence time more homogeneous the Py-C deposition rate was obtained along the reaction chamber axis. Finally, a CVD and CVI theoretical modelling was performed.