Frictional Instabilities and Carbonation of Basalts Triggered by Injection of Pressurized H2O- and CO2- Rich Fluids

The safe application of geological carbon storage depends also on the seismic hazard associated with fluid injection. In this regard, we performed friction experiments using a rotary shear apparatus on precut basalts with variable degree of hydrothermal alteration by injecting distilled H2O, pure CO2, and H2O + CO2fluid mixtures under temperature, fluid pressure, and stress conditions relevant for large-scale subsurface CO2storage reservoirs. In all experiments, seismic slip was preceded by short-lived slip bursts. Seismic slip occurred at equivalent fluid pressures and normal stresses regardless of the fluid injected and degree of alteration of basalts. Injection of fluids caused also carbonation reactions and crystallization of new dolomite grains in the basalt-hosted faults sheared in H2O + CO2fluid mixtures. Fast mineral carbonation in the experiments might be explained by shear heating during seismic slip, evidencing the high chemical reactivity of basalts to H2O + CO2mixtures

The role of fault rock fabric in the dynamics of laboratory faults

Fault stability is inherently linked to the frictional and healing properties of fault rocks and associated fabrics. Their complex interaction controls how the stored elastic energy is dissipated, that is, through creep or seismic motion. In this work, we focus on the relevance of fault fabrics in controlling the reactivation and slip behavior of dolomite-anhydrite analog faults. We designed a set of laboratory experiments where we first develop fault rocks characterized by different grain size reduction and localization at normal stresses of σN = 15, 35, 60, and 100 MPa and second, we reload and reactivate these fault rocks at the frictional stability transition, achieved at σN = 35 MPa by reducing the machine stiffness. If normal stress is lowered this way, reactivation occurs with relatively large stress drops and large peak-slip velocities. Subsequent unstable behavior produces slow stick-slip events with low stress drop and with either asymmetric or Gaussian slip velocity function depending on the inherited fault fabric. If normal stress is raised, deformation is accommodated within angular cataclasites promoting stable slip. The integration of microstructural data (showing brittle reworking of preexisting textures) with mechanical data (documenting restrengthening and dilation upon reactivation) suggests that frictional and chemically assisted healing, which is common in natural faults during the interseismic phase, can be a relevant process in developing large instabilities. We also conclude that fault rock heterogeneity (fault fabric) modulates the slip velocity function and thus the dynamics of repeating stick-slip cycles

Sector-zoned clinopyroxene as a recorder of magma history, eruption triggers, and ascent rates

Sector-zoned clinopyroxene is common in igneous rocks, but has been overlooked in the study of magmatic processes. Whilst concentric zoning is commonly used as a record of physicochemical changes in the melt feeding crystal growth, clinopyroxene is also highly sensitive to crystallisation kinetics. In sector-zoned crystals, the fidelity of compositional changes as recorders of magma history is dubious and the interplay between thermodynamic and kinetic controls remains poorly understood. Here we combine electron probe and laser ablation micro-chemical maps of titanaugite crystals from Mt. Etna (Sicily, Italy) to explore the origin of sector zoning at the major and trace element levels, and its implications for the interpretation of magmatic histories. Elemental maps afford the possibility to revisit sector zoning from a spatially controlled perspective. The most striking observation is a clear decoupling of elements into sectors vs. concentric zones within single crystals. Most notably, Al-Ti enrichments and Si-Mg depletions in the prism sectors {1 0 0}, {1 1 0} and {0 1 0} relative to the hourglass (or basal) sectors {−1 1 1} correlate with enrichments in rare earth elements and highly charged high field strength elements due to cation exchanges driven by kinetic effects. In contrast, transition metals (Cr, Ni, Sc) show little partitioning into sectors and strong enrichments in concentric zones following resorbed surfaces, interpreted as evidence of mafic recharge and magma mixing. Our results document that kinetic partitioning has minor effects on the compositional variations of cations with low charge relative to the ideal charge/radius of the structural site they occupy in the clinopyroxene lattice. We suggest that this may be due to a lower efficiency in charge balance mechanisms compared to highly charged cations. It follows that compatible metals such as Cr can be considered trustworthy recorders of mafic intrusions and eruption triggers even in sector-zoned crystals. We also observe that in alkaline systems where clinopyroxene crystallisation takes place at near-equilibrium conditions, sector zoning should have little effect on Na-Ca partitioning and in turn, on the application of experimentally calibrated thermobarometers. Our data show that whilst non-sector-zoned crystals form under relatively stagnant conditions, sector zoning develops in response to low degrees of undercooling, such as during slow magma ascent. Thus, we propose that the chemistry of sector-zoned crystals can provide information on magma history, eruption triggers, and possibly ascent rates

The Onset and Solidification Path of a Basaltic Melt by in situ Differential Scanning Calorimetry (DSC) and ex situ Investigations

The in situ differential scanning calorimetry (DSC) technique has been applied to investigate the solidification paths of a basaltic liquid. The starting glass was heated up to 1300°C, kept at this superliquidus temperature for 2 h and cooled at rates (ΔT/Δt) of 7, 60, 180, 1000, and 1800°C/h, down to 800 and 600°C. Glass transition temperature (Tg), crystallization temperature (Tx_HR) and melting temperature (Tm) were measured by in situ DSC spectra on heating. Tx measured along the cooling paths (Tx_CR) shows exothermic peaks that change from a single symmetric shape (7 and 60°C/h) to multi-component patterns (180, 1000, and 1800°C/h). The recovered products characterized by field emission gun source of the scanning electron microscopy and electron probe micro-analyzer-wavelength dispersive spectrometers show a phase assemblage of spinel (sp), clinopyroxene (cpx), melilite (mel), plagioclase (plg), and glass. Moreover, crystal size distributions (CSDs) and growth rates (Gmax and GCSD) were also determined. The crystal content slightly increases from 7 to 1800°C/h. Faceted sp are present in all the run products with an amount always <2 area%. Cpx increases from 7 to 1800°C/h, changing its texture from almost faceted to dendritic between 60 and 180°C/h. The area% of mel follows an asymmetric Gaussian trend, while plg nucleates only at 7°C/h with a content <2 area%. The coupling of DSC and SEM outcomes indicate that sp nucleate first, followed by cpx and mel (and/or plg). The increment of ΔT/Δt causes an increase of the CSD slope (m) and crystal population density per size (n0), as well as a decrease of the crystal size, for both cpx and sp. The log-linear CSD segments with different slopes at 7 and 60°C/h suggest multiple nucleation events and crystal growth by coarsening. Gmax and GCSD for cpx and sp directly measured on the actual crystallization time by DSC spectra, both increase with the increasing of ΔT/Δt. The onset temperature of crystallization (Txi) decreases as ΔT/Δt increases, following an exponential trend that defines the uppermost portion of a time-transformation-temperature-like curve. This analytical model allows us to quantitatively model the kinetic crystallization paths of dry basalts

A multi-methodological approach to record dynamics and timescales of the plumbing system of Zaro (Ischia Island, Italy)

Determining the time spans of processes related to the assembly of eruptible magma at active volcanoes is fundamental to understand magma chamber dynamics and assess volcanic hazard. This information can be recorded in the chemical zoning of crystals. Nevertheless, this kind of study is still poorly employed for the active volcanoes of the Neapolitan area (Southern Italy), in particular, for Ischia island where the risk is extremely high and this information can provide the basis for probabilistic volcanic hazard assessment. For these reasons, we acquired chemical composition on clinopyroxene crystals erupted at Ischia during the Zaro eruption (6.6 ± 2.2 ka) and performed numerical simulations of the input of mafic magma into a trachytic reservoir, in order to investigate various aspects of pre-eruptive dynamics occurring at different timescales. This event emplaced a ~ 0.1 km3 lava complex, in which the main trachytic lava flows host abundant mafic to felsic enclaves. Previous petrological investigation suggested that mafic magma(s) mixed/mingled with a trachytic one, before the eruption. In this work, the clinopyroxene zoning patterns depict the growth of crystals in different magmatic environments, recording sequential changes occurred in the plumbing system before the eruption. The evolution of the plumbing system involved a hierarchy of timescales: a few hours for magma mingling caused by mafic recharge(s) and likely occurred multiple times over a decade during which a dominant magmatic environment was sustained before the eruption. Such timescales must be considered in volcanic hazard assessment at Ischia and similar active volcanoes in densely populated areas

Frictional Instabilities and Carbonation of Basalts Triggered by Injection of Pressurized H2O- and CO2- Rich Fluids

The safe application of geological carbon storage depends also on the seismic hazard associated with fluid injection. In this regard, we performed friction experiments using a rotary shear apparatus on precut basalts with variable degree of hydrothermal alteration by injecting distilled H2O, pure CO2, and H2O + CO2 fluid mixtures under temperature, fluid pressure, and stress conditions relevant for large-scale subsurface CO2 storage reservoirs. In all experiments, seismic slip was preceded by short-lived slip bursts. Seismic slip occurred at equivalent fluid pressures and normal stresses regardless of the fluid injected and degree of alteration of basalts. Injection of fluids caused also carbonation reactions and crystallization of new dolomite grains in the basalt-hosted faults sheared in H2O + CO2 fluid mixtures. Fast mineral carbonation in the experiments might be explained by shear heating during seismic slip, evidencing the high chemical reactivity of basalts to H2O + CO2 mixtures

Unravelling the effect of undercooling on (dis)equilibrium textures and compositions of basaltic magmas

Undercooling and crystallization kinetics are recognized increasingly as important processes controlling the final textures and compositions of minerals as well as the physicochemical state of magmas during ascent and emplacement. Within a single volcanic unit, phenocrysts, microphenocrysts and microlites can span a wide range of compositions, develop complex zoning patterns, and show intricate textures testifying to crystallization far from equilibrium. These petrographic complexities are not associated necessarily with magma chamber processes such as mixing or mingling of distinctly different bulk compositions but, rather, may be caused by kinetic effects controlling the crystal growth and magma evolution. Heat-dissipation and decompression are the most effective driving forces of cooling and volatile loss that, in turn, exert a primary control on the solidification path of the bulk system (i.e., crystal and melt). Understanding these kinetic aspects over the temporal and spatial scales at which volcanic processes occur is therefore essential to interpret correctly the time-varying environmental conditions recorded in igneous minerals. This PhD thesis aims to summarize and integrate experimental and natural studies pertaining to the crystallization of magmas along kinetic or time-dependent pathways, where solidification is driven by changes in temperature, pressure and volatile concentration. Fundamental concepts examined in the last decades include the effect of undercooling on crystal nucleation and growth, as well as on the transition between interface- and diffusion-controlled crystal growth and mass transfer occurring after crystals stop growing. In this thesis, static and dynamic crystallization processes are investigated for natural trachybasaltic-trachyandesitic products typically of the magmatic activity at Mt. Etna volcano (Sicily, Italy). By decoding the textural and compositional information within crystalline phases, it is possible to place quantitative constraints on the crustal transport, ascent and emplacement histories of erupted magmas. Here, I present a collection of three papers that has been published in some of the most respected peer-reviewed journals for mineralogy, petrology, geochemistry and volcanology, i.e., Chemical Geology (first paper), Geochimica et Cosmochimica Acta (second paper) and Minerals (third paper). More specifically, magma crystallization under dynamic conditions has been assessed through isothermal time-series experiments on clinopyroxene, illustrated in the first paper reported in the following thesis. In this work a variety of departures from polyhedral growth, including morphologies indicating crystal surface instability, dendritic structures, sector zoning and growth twins are linked to the rate at which crystals grow. These have implications for the entrapment of melt inclusions and plausibility for interpreting the growth chronology of individual crystals. In the second paper, deviation from chemical equilibrium, developed in response to kinetically controlled cation redistributions and related to the partitioning of major and trace elements between clinopyroxene and melt, has been evaluated by the analysis of hourglass sector-zoned phenocrysts based on equilibrium and thermodynamic principles. In the third paper, the crystallization conditions of a sill-like intrusion at Mt. Etna volcano have been elucidated by integrating major cation exchanges in clinopyroxene, plagioclase and titanomagnetite, thereby providing decompression, degassing and geospeedometric constrains on the emplacement conditions of magma. All the aforementioned papers were carried out in team, but I have contributed either in designing and performing both the experiments and analyses, or in interpreting the acquired data and in writing the original manuscripts

Rock magnetic and micro-morphological analysis on snow deposits: recognition of anthropogenic origin of particulate matter in urban and wilderness areas (central Italy)

Low field magnetic susceptibility and other rock magnetic analyses are applied to inspect the magnetic nature of solid residuals in snow samples collected in downtown Rome and in two Natural Parks in central Italy. Field emission scanning electron microscope and energy dispersive spectroscopy (FESEM-EDS) analyses are utilized to reveal the nature of Fe-rich particles and discriminate their anthropogenic origin. The results indicate that magnetite (Fe3O4) is the main magnetic carrier in almost all samples and that the variations in concentration are directly associated with local sources of particulate matter (PM) from anthropogenic pollution related to automotive circulation in both environments. Magnetic minerals of other provenance are found as accessories. The snow deposits revealed to be an efficient neutral tool for fine particle collections, also in environments characterized by different concentration and source of pollutants

Solidification of a rhyolitic magma beneath the Krafla caldera

A shallow, silica-rich rhyolitic magma body was drilled during the perforation of the Krafla caldera, carried out in the framework of the Iceland Deep Drilling Project (IDDP). Samples of the rhyolitic magma were collected among the cuttings brought to the surface by the drilling fluids. These samples consist of vesiculated glassy fragments containing crystals of titanomagnetite, plagioclase and clinopyroxene. Minerals are in textural and chemical disequilibrium with the rhyolitic melt, as indicated by compositional zoning of plagioclase and exsolution lamellae in clinopyroxene. Additionally, Fe-Mg exchange between clinopyroxene and melt (cpx-meltKDFe-Mg) and Ab-An exchange between plagioclase and melt (plg-meltKDAb-An) show values much lower than those expected at equilibrium conditions. These disequilibrium features make difficult to assess correctly the crystallization path of magma through a classical approach based on the use of geotherbarometers or thermodynamic modelling. Therefore, in order to elucidate the physico-chemical conditions controlling the final stage of magmatic evolution, we aim to investigate experimentally the origin of the rhyolitic magma, which is still under debate. Indeed, the change of the crystallization conditions recorded by minerals may be addressed either to rapid extraction of the rhyolitic melt from a crystal mush, or to slow cooling of the rhyolitic melt produced in-situ by partial melting of the host felsite rock