Soil organic carbon dynamics under perennial energy crops

The European renewable energy directive 2009/28/EC (E.C. 2009) provides a legislative framework for reducing GHG emissions by 20%, while achieving a 20% share of energy from renewable sources by 2020. Perennial energy crops could significantly contribute to limit GHG emissions through replacing equivalent fossil fuels and by sequestering a considerable amount of carbon into the soil through the large amounts of belowground biomass produced. The objective of this study is to evaluate the effects of land use change that perennial energy crops have on croplands (switchgrass) and marginal grasslands (miscanthus). For that purpose above and belowground biomass, SOC variation and Net Ecosystem Exchange were evaluated after five years of growth. At aboveground level both crops produced high biomass under cropland conditions as well as under marginal soils. At belowground level they also produced large amounts of biomass, but no significant influences on SOC in the upper layer (0-30 cm) were found. This is probably because of the "priming effect" that caused fast carbon substitution. In switchgrass only it was found a significant SOC increase in deeper layers (30-60 cm), while in the whole soil profile (0-60 cm) SOC increased from 42 to 51 ha-1. However, the short experimental periods (for both switchgrass and miscanthus), in which land use change was evaluated, do not permit to determine the real capacity of perennial energy crops to accumulate SOC. In conclusion the large amounts of belowground biomass enhanced the SOC dynamic through the priming effect resulting in increased SOC in cropland but not in marginal grassland.

Numerical simulations of magma chamber dynamics at Campi Flegrei, and associated seismicity, deformation and gravity changes

Understanding the complex relationships between quantities measured by volcanic monitoring network and shallow magma processes is a crucial headway for the comprehension of volcanic processes and a more realistic evaluation of the associated hazard. This question is very relevant at Campi Flegrei, a volcanic quiescent caldera immediately north-west of Napoli (Italy). The system activity shows a high fumarole release and periodic ground slow movement (bradyseism) with high seismicity. This activity, with the high people density and the presence of military and industrial buildings, makes Campi Flegrei one of the areas with higher volcanic hazard in the world. In such a context my thesis has been focused on magma dynamics due to the refilling of shallow magma chambers, and on the geophysical signals detectable by seismic, deformative and gravimetric monitoring networks that are associated with this phenomenologies. Indeed, the refilling of magma chambers is a process frequently occurring just before a volcanic eruption; therefore, the faculty of identifying this dynamics by means of recorded signal analysis is important to evaluate the short term volcanic hazard. The space-time evolution of dynamics due to injection of new magma in the magma chamber has been studied performing numerical simulations with, and implementing additional features in, the code GALES (Longo et al., 2006), recently developed and still on the upgrade at the Istituto Nazionale di Geofisica e Vulcanologia in Pisa (Italy). GALES is a finite element code based on a physico-mathematical two dimensional, transient model able to treat fluids as multiphase homogeneous mixtures, compressible to incompressible. The fundamental equations of mass, momentum and energy balance are discretised both in time and space using the Galerkin Least-Squares and discontinuity-capturing stabilisation technique. The physical properties of the mixture are computed as a function of local conditions of magma composition, pressure and temperature.The model features enable to study a broad range of phenomenologies characterizing pre and sin-eruptive magma dynamics in a wide domain from the volcanic crater to deep magma feeding zones. The study of displacement field associated with the simulated fluid dynamics has been carried out with a numerical code developed by the Geophysical group at the University College Dublin (O’Brien and Bean, 2004b), with whom we started a very profitable collaboration. In this code, the seismic wave propagation in heterogeneous media with free surface (e.g. the Earth’s surface) is simulated using a discrete elastic lattice where particle interactions are controlled by the Hooke’s law. This method allows to consider medium heterogeneities and complex topography. The initial and boundary conditions for the simulations have been defined within a coordinate project (INGV-DPC 2004-06 V3_2 “Research on active volcanoes, precursors, scenarios, hazard and risk - Campi Flegrei”), to which this thesis contributes, and many researchers experienced on Campi Flegrei in volcanological, seismic, petrological, geochemical fields, etc. collaborate. Numerical simulations of magma and rock dynamis have been coupled as described in the thesis. The first part of the thesis consists of a parametric study aimed at understanding the eect of the presence in magma of carbon dioxide in magma in the convection dynamics. Indeed, the presence of this volatile was relevant in many Campi Flegrei eruptions, including some eruptions commonly considered as reference for a future activity of this volcano. A set of simulations considering an elliptical magma chamber, compositionally uniform, refilled from below by a magma with volatile content equal or dierent from that of the resident magma has been performed. To do this, a multicomponent non-ideal magma saturation model (Papale et al., 2006) that considers the simultaneous presence of CO2 and H2O, has been implemented in GALES. Results show that the presence of CO2 in the incoming magma increases its buoyancy force promoting convection ad mixing. The simulated dynamics produce pressure transients with frequency and amplitude in the sensitivity range of modern geophysical monitoring networks such as the one installed at Campi Flegrei . In the second part, simulations more related with the Campi Flegrei volcanic system have been performed. The simulated system has been defined on the basis of conditions consistent with the bulk of knowledge of Campi Flegrei and in particular of the Agnano-Monte Spina eruption (4100 B.P.), commonly considered as reference for a future high intensity eruption in this area. The magmatic system has been modelled as a long dyke refilling a small shallow magma chamber; magmas with trachytic and phonolitic composition and variable volatile content of H2O and CO2 have been considered. The simulations have been carried out changing the condition of magma injection, the system configuration (magma chamber geometry, dyke size) and the resident and refilling magma composition and volatile content, in order to study the influence of these factors on the simulated dynamics. Simulation results allow to follow each step of the gas-rich magma ascent in the denser magma, highlighting the details of magma convection and mixing. In particular, the presence of more CO2 in the deep magma results in more ecient and faster dynamics. Through this simulations the variation of the gravimetric field has been determined. Afterward, the space-time distribution of stress resulting from numerical simulations have been used as boundary conditions for the simulations of the displacement field imposed by the magmatic dynamics on rocks. The properties of the simulated domain (rock density, P and S wave velocities) have been based on data from literature on active and passive tomographic experiments, obtained through a collaboration with A. Zollo at the Dept. of Physics of the Federici II Univeristy in Napoli. The elasto-dynamics simulations allow to determine the variations of the space-time distribution of deformation and the seismic signal associated with the studied magmatic dynamics. In particular, results show that these dynamics induce deformations similar to those measured at Campi Flegrei and seismic signals with energies concentrated on the typical frequency bands observed in volcanic areas. The present work shows that an approach based on the solution of equations describing the physics of processes within a magmatic fluid and the surrounding rock system is able to recognise and describe the relationships between geophysical signals detectable on the surface and deep magma dynamics. Therefore, the results suggest that the combined study of geophysical data and informations from numerical simulations can allow in a near future a more ecient evaluation of the short term volcanic hazard.

The coupling between electron transfer and Protein/Solvent Dynamics in Photosynthetic Reaction Centers: Spectroscopic Studies in Amorphous Matrices

We investigated at the molecular level protein/solvent interactions and their relevance in protein function through the use of amorphous matrices at room temperature. As a model protein, we used the bacterial photosynthetic reaction center (RC) of Rhodobacter sphaeroides, a pigment protein complex which catalyzes the light-induced charge separation initiating the conversion of solar into chemical energy. The thermal fluctuations of the RC and its dielectric conformational relaxation following photoexcitation have been probed by analyzing the recombination kinetics of the primary charge-separated (P+QA-) state, using time resolved optical and EPR spectroscopies. We have shown that the RC dynamics coupled to this electron transfer process can be progressively inhibited at room temperature by decreasing the water content of RC films or of RC-trehalose glassy matrices. Extensive dehydration of the amorphous matrices inhibits RC relaxation and interconversion among conformational substates to an extent comparable to that attained at cryogenic temperatures in water-glycerol samples. An isopiestic method has been developed to finely tune the hydration level of the system. We have combined FTIR spectral analysis of the combination and association bands of residual water with differential light-minus-dark FTIR and high-field EPR spectroscopy to gain information on thermodynamics of water sorption, and on structure/dynamics of the residual water molecules, of protein residues and of RC cofactors. The following main conclusions were reached: (i) the RC dynamics is slaved to that of the hydration shell; (ii) in dehydrated trehalose glasses inhibition of protein dynamics is most likely mediated by residual water molecules simultaneously bound to protein residues and sugar molecules at the protein-matrix interface; (iii) the local environment of cofactors is not involved in the conformational dynamics which stabilizes the P+QA-; (iv) this conformational relaxation appears to be rather delocalized over several aminoacidic residues as well as water molecules weakly hydrogen-bonded to the RC.

N-Heterocyclic carbene complexes of rhodium: structures, dynamics and catalysis

A series of imidazolium salts of the type [BocNHCH2CH2ImR]X (Boc = t-Bu carbamates; Im = imidazole) (R = Me, X = I, 1a; R = Bn, X = Br, 1b; R = Trityl, X = Cl, 1c) and [BnImR’]X (R’ = Me, X = Br, 1d; R’ = Bn, X = Br, 1e; R’ = Trityl, X = Cl, 1g; R’ = tBu, X = Br, 1h) bearing increasingly bulky substituents were synthetized and characterized. Subsequently, these precursors were employed in the synthesis of silver(I)-N-heterocyclic (NHC) complexes as transmetallating reagents for the preparation of rhodium(I) complexes [RhX(NBD)(NHC)] (NHC = 1-(2-NHBoc-ethyl)-3-R-imidazolin-2-ylidene; X = Cl; R = Me, 4a; R = Bn, 4b; R = Trityl, 4c; X = I, R = Me, 5a; NHC = 1-Bn-3-R’-imidazolin-2-ylidene; X = Cl; R’ = Me, 4d, R’ = Bn, 4e, R’ = Trityl, 4g; R’ = tBu, 4h). VT NMR studies of these complexes revealed a restricted rotation barriers about the metal-carbene bond. While the rotation barriers calculated for the complexes in which R = Me, Bn (4a,b,d,e and 5a) matched the experimental values, this was not true for the complexes 4c,g, bearing a trityl group for which the values are much smaller than the calculated ones. Energy barriers for 4c,g, derived from a line shape simulation, showed a strong dependence on the temperature while for 4h the rotational energy barrier is stopped at room temperature. The catalytic activity of the new rhodium compounds was investigated in the hydrosilylation of terminal alkynes and in the addition of phenylboronic acid to benzaldehyde. The imidazolium salts 1d,e were also employed in the synthesis of new iron(II)-NHC complexes. Finally, during a six-months stay at the University of York a new ligand derived from Norharman was prepared and employed in palladium-mediated cross-coupling.

Evaluation of energy level to be absorbed by tractor ROPS: Actual Tests, Simulation and Computation

A highly dangerous situations for tractor driver is the lateral rollover in operating conditions. Several accidents, involving tractor rollover, have indeed been encountered, requiring the design of a robust Roll-Over Protective Structure (ROPS). The aim of the thesis was to evaluate tractor behaviour in the rollover phase so as to calculate the energy absorbed by the ROPS to ensure driver safety. A Mathematical Model representing the behaviour of a generic tractor during a lateral rollover, with the possibility of modifying the geometry, the inertia of the tractor and the environmental boundary conditions, is proposed. The purpose is to define a method allowing the prediction of the elasto-plastic behaviour of the subsequent impacts occurring in the rollover phase. A tyre impact model capable of analysing the influence of the wheels on the energy to be absorbed by the ROPS has been also developed. Different tractor design parameters affecting the rollover behaviour, such as mass and dimensions, have been considered. This permitted the evaluation of their influence on the amount of energy to be absorbed by the ROPS. The mathematical model was designed and calibrated with respect to the results of actual lateral upset tests carried out on a narrow-track tractor. The dynamic behaviour of the tractor and the energy absorbed by the ROPS, obtained from the actual tests, showed to match the results of the model developed. The proposed approach represents a valuable tool in understanding the dynamics (kinetic energy) and kinematics (position, velocity, angular velocity, etc.) of the tractor in the phases of lateral rollover and the factors mainly affecting the event. The prediction of the amount of energy to be absorbed in some cases of accident is possible with good accuracy. It can then help in designing protective structures or active security devices.

Modelling UV response of biomolecules: from electronic structure to ab-initio dynamics.

The interaction of organic chromophores with light initiates ultrafast processes in the timescale of femtoseconds. An atomistic understanding of the mechanism driving such photoinduced reactions opens up the door to exploit them for our benefit. This thesis studies the interactions of ultraviolet light with the DNA/RNA molecules and the amino-acid tryptophan. Using some of the most accurate electronic structure methods and sophisticated environmental modelling, the works documented herein enable quantitative comparisons with cutting-edge experimental data. The relaxation pathways undertaken by the excited molecule are revealed through static and dynamical investigations of the excited-state potential energy surface. The profound role played by the dynamic response of the environment to guide the excitation in these timescales is addressed thoroughly.

Simulation of photoinduced processes in organic chromophores: mapping photochemically relevant states for accurate dynamics

The simulation of ultrafast photoinduced processes is a fundamental step towards the understanding of the underlying molecular mechanism and interpretation/prediction of experimental data. Performing a computer simulation of a complex photoinduced process is only possible introducing some approximations but, in order to obtain reliable results, the need to reduce the complexity must balance with the accuracy of the model, which should include all the relevant degrees of freedom and a quantitatively correct description of the electronic states involved in the process. This work presents new computational protocols and strategies for the parameterisation of accurate models for photochemical/photophysical processes based on state-of-the-art multiconfigurational wavefunction-based methods. The required ingredients for a dynamics simulation include potential energy surfaces (PESs) as well as electronic state couplings, which must be mapped across the wide range of geometries visited during the wavepacket/trajectory propagation. The developed procedures allow to obtain solid and extended databases reducing as much as possible the computational cost, thanks to, e.g., specific tuning of the level of theory for different PES regions and/or direct calculation of only the needed components of vectorial quantities (like gradients or nonadiabatic couplings). The presented approaches were applied to three case studies (azobenzene, pyrene, visual rhodopsin), all requiring an accurate parameterisation but for different reasons. The resulting models and simulations allowed to elucidate the mechanism and time scale of the internal conversion, reproducing or even predicting new transient experiments. The general applicability of the developed protocols to systems with different peculiarities and the possibility to parameterise different types of dynamics on an equal footing (classical vs purely quantum) prove that the developed procedures are flexible enough to be tailored for each specific system, and pave the way for exact quantum dynamics with multiple degrees of freedom.

Inequality of income and poverty persistence in the Municipality of Bologna: a cross-sectional and longitudinal analysis through administrative data

This work is part of a project promoted by Emilia-Romagna that aims at encouraging research activities in order to support the innovation strategies of the regional economic system through the exploitation of new data sources. To gain this scope, a database containing administrative data is provided by the Municipality of Bologna. This is achieved by linking data from the Register Office of the Municipality and fiscal data coming from the tax returns submitted to the Revenue Agency and released by the Ministry of Economy and Finance for the period 2002-2017. The main purpose of the project is the analysis of the medium term financial and distributional trends of income of the citizens residing in the Municipality of Bologna. Exploiting this innovative source of data allow us to analyse the dynamics of income at municipal level, overcoming the lack of information in official survey-based statistic. We investigate these trends by building inequality indicators and by examining the persistence of in-work poverty. Our results represent an important informative element to improve the effectiveness and equity of welfare policies at the local level, and to guide the distribution of economic and social support and urban redevelopment interventions in different areas of the Municipality.

Oceanic Near-inertial internal waves generation, propagation and interaction with mesoscale dynamics

Oceans play a key role in the climate system, being the largest heat sinks on Earth. Part of the energy balance of ocean circulation is driven by the Near-inertial internal waves (NIWs). Strong NIWs are observed during a multi-platform, multi-disciplinary and multi-scale campaign led by the NATO-STO CMRE in autumn 2017 in the Ligurian Sea (northwestern Mediterranean Sea). The objectives of this work are as follows: characterise the studied area at different scales; study the NIWs generation and their propagation; estimate the NIWs properties; study the interaction between NIWs and mesoscale structures. This work provides, to the author’s knowledge, the first characterization of NIWs in the Mediterranean Sea. The near-surface NIWs observed at the fixed moorings are locally generated by wind bursts while the deeper waves originate in other regions and arrive at the moorings several days later. Most of the observed NIWs energy propagates downward with a mean vertical group velocity of (2.2±0.3) ⋅10-4 m s-1. On average, the NIWs have an amplitude of 0.13 m s-1 and mean horizontal and vertical wavelengths of 43±25 km and 125±35 m, while shorter wavelengths are observed at the near-coastal mooring, 36±2 km and 33±2 m, respectively. Most of the observed NIWs are blue shifted and reach a value 9% higher than the local inertial frequency. Only two observed NIWs are characterised by a redshift (up to 3% lower than the local inertial frequency). In support of the in situ observations, a high resolution numerical model is implemented using NEMO (Madec et al., 2019). Results show that anticyclones (cyclones) shift the frequency of NIWs to lower (higher) frequencies with respect to the local inertial frequency. Anticyclones facilitate the downward propagation of NIW energy, while cyclones dampen it. Absence of NIWs energy within an anticyclone is also investigated.