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.

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.

Fellow travelers: an ethnographic study of the dynamics of inter-organizational collaboration

The research is a 13-months ethnographic field work on the early operations of a Multi-party alliance active in the global field of indoor positioning. The study aims to understand and investigate empirically the challenges that at the individual and group level influence the organizing principle guiding the alliance operations and evolution. Its contribution rests on the dynamics affecting ecosystems of innovation and collaborative spaces of value co-creation in inter-organizational projects.

Dynamics of terricolous alpine lichen communities of the Alps and Mediterranean Mountains in a climate change perspective

This thesis focuses on the impact of climate change in alpine ecosystems stressing the response of high elevation terricolous lichen communities. In fact, despite the strong sensitivity of cryptogams to changes in climatic factors, information is still scanty.We collected records in 154 plots placed in the summit area of the Majella Massif. In Following a multitaxon approach, Chapter 1 includes cryptogams and vascular plants. We analysed patterns in species richness, beta diversity and functional composition. In Chapter 2, we analysed the relationships between climatic variables and phylogenetic diversity and structure indices. Chapter 3 provides a long-term response relative to the consequences of climate change on a representative terricolous lichen genus across the Alps. Chapter 4 explores the relationships between the species richness and the functional composition of lichen growing on two types of substrates (carbonatic and siliceous soils) along different elevation gradients in the Eastern Alps. Climate change could affect cryptogams and lichens much more than vascular plants in Mediterranean mountains. Contrasting species-climate and traits-climate relationships were found between lichens and bryophytes, suggesting that each group may be sensitive to different components of climate change. Ongoing climate change may also lead to a loss of genetic diversity at high elevation ranges in the Mediterranean mountains, pauperising the life history richness of lichens. Alpine results forecasted that moderate range loss dynamics will occur at low elevation and in peripheral areas of the alpine chain. Results also support the view that range dynamics could be associated with functional traits mainly related to water-use strategies, dispersal, and establishment ability. We also highlighted the importance of substrates as a main driver of both species’ richness and functional traits composition. A “trade-off” also occurs between stress tolerance and the competitive response of communities of terricolous lichens that grow above siliceous and carbonatic soils.

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.