Pontesilli, Alessio

We present undercooling (∆T) experiments aimed at investigating the effect of growth kinetics on the textural and compositional evolution of clinopyroxene crystals growing from a high-K basalt erupted during the 2003 paroxysm of Stromboli volcano (Italy). The experiments were performed at P = 350 MPa, T = 1050–1210 °C, H2Omelt = 0–3 wt%, and fO2 = Ni-NiO + 1.5 buffer. An initial stage of supersaturation was imposed to the melt under nominally anhydrous (∆Tanh = 10–150 °C) and hydrous (∆Thyd = 25–125 °C) conditions. Afterwards, this supersaturation state was mitigated by melt relaxation phenomena over an annealing time of 24 h. Results show that plagioclase is the liquidus mineral phase of the high-K basalt at ∆Tanh = 10 °C and dominates the phase assemblage as the degree of undercooling increases. Conversely, clinopyroxene and spinel co-saturate the melt at ∆Thyd = 25 °C, followed by the subordinate formation of plagioclase. At ∆Tanh/hyd ≤ 50 °C, the textural maturation of clinopyroxene produces polyhedral crystals with {−111} (hourglass) and {hk0} (prism) sectors typical of a layer-by-layer growth mechanism governed by an interface-controlled crystallization regime. At ∆Tanh/hyd ≥ 75 °C, the attainment of dendritic and skeletal morphologies testifies to the establishment of diffusion-limited reactions at the crystal-melt interface. 3D reconstructions of synchrotron radiation X-ray microtomographic data reveal a composite growth history for clinopyroxene crystals obtained at ∆Tanh/hyd ≥ 95 °C. The early stage of melt supersaturation produces rosette-like structures composed of dendritic branches of clinopyroxene radiating from a common spinel grain, which acts as surface for heterogeneous nucleation. As diffusive relaxation phenomena progress over the annealing time, the elongate dendrites that constitute the inner crystal domain are partially infilled by the melt and develop skeletal overgrowths in the outer domain. With the increasing degree of undercooling, TAl and M1Ti cations are progressively incorporated in the lattice site of clinopyroxene at the expense of TSi and M1Mg cations. Because of the effect of H2Omelt on the liquidus depression and melt depolymerization, crystals obtained at ∆Thyd are also more enriched in TAl and M1Ti and depleted in TSi and M1Mg than those growing at ∆Tanh. The emerging picture is that the morphological and geochemical evolution of clinopyroxene is mutually controlled by the combined effects of melt supersaturation and relaxation phenomena. A new empirical relationship based on the cation exchange reactions in the lattice site of clinopyroxene is finally proposed to estimate the degree of undercooling governing the crystallization of augitic phenocrysts erupted during normal and violent explosions at Stromboli.

Petrological studies of active volcanoes typically focus on eruptive phenomena occurring over long timescales of the order of days to years, aiming at identifying major changes in the physico-chemical state of magma during ascent towards the surface. Exceptionally, we present results from an integrated petrological and statistical approach based on the compilation of ∼5300 major and trace element data for glass and crystals, in combination with volcanological data on eruptive events occurred over timescales of minutes at Stromboli volcano (Sicily). On May 11, 2019, we had the rare opportunity to collect individual fresh fallout ash products from eighteen mostly consecutive explosions, erupted in a 2-h time span and, at the same time, to acquire continuous high frequency (50 Hz) infrared thermal data of the same explosions. Through video analysis, we observe that explosions were more frequent and ash-dominated at the southwestern crater area (SCA, 8–10 events/h) than at the northeastern crater area (NCA, 3–5 events/h), where coarser material was ejected. The statistical analysis of glass and plagioclase compositions reveals differences in the products erupted from the two crater areas. SCA explosions tapped less differentiated magmas (Mg#∼42–46, ∼257–365 LaN, ∼0.7–0.9 Eu/Eu*) in equilibrium with more anorthitic plagioclase cores (An∼72–88), whereas NCA area explosions are more differentiated (Mg#∼40–44, ∼286–387 LaN, ∼0.6–0.8 Eu/Eu*) and in equilibrium with less anorthitic plagioclase cores (An∼68–82). Thermometric calculations based on major and trace element clinopyroxene-plagioclase-melt equilibrium modeling highlight that the SCA explosions were statistically fed by hotter magmas in comparison to NCA explosions. Plagioclase-based diffusion modeling also indicates longer timescales for the dynamic ascent of NCA magmas, leading to preferential groundmass crystallization at the conduit walls and transition from sideromelane to tachylite groundmass textures. The final emerging picture is that in May 2019, concurrent normal eruptions from different crater areas at Stromboli were heralds of compositionally and thermally diverse magmas rising at different rates within the uppermost branched part of the conduit region. High frequency petrological investigations aided by statistical treatment of data have the potential to constrain dynamic conduit processes related to transient, explosive eruptions in persistently active volcanoes, thereby offering new insights on the interplay between magma dynamics, ascent timescales, and eruptive behavior.

Thermobarometry provides a critical means of assessing locations of magma storage and dynamics in the lead-up to volcanic eruptions and crustal growth. A common approach is to utilise minerals that have compositions sensitive to changes in pressure and/or temperature, such as clinopyroxene, which is ubiquitous in mafic to intermediate magmas. However, clinopyroxene thermobarometry may carry significant uncertainty and require an appropriate equilibrium melt composition. In addition, the degree of magma undercooling (ΔT) affects clinopyroxene composition and zoning, with common sector zoning potentially obfuscating thermobarometry results. Here, we use a set of crystallisation experiments on a primitive trachybasalt from Mt. Etna (Italy) at ΔT = 25–233 °C, P = 400–800 MPa, H2O = 0–4 wt % and fO2 = NNO + 2, with clinopyroxene crystals defined by Al-rich zones (prisms and skeletons) and Al-poor zones (hourglass and overgrowths) to assess common equilibrium models and thermobarometric approaches. Under the studied conditions, our data suggest that the commonly applied Fe–Mg exchange (cpx-meltKdFe–Mg) is insensitive to increasing ΔT and may not be a reliable indicator of equilibrium. The combined use of DiHd (CaMgSi2O6 + CaFeSi2O6) and EnFs (Mg2Si2O6 + Fe2Si2O6) models indicate the attainment of equilibrium in both Al-rich and Al-poor zones for almost all investigated ΔT. In contrast, CaTs (CaAl2SiO6) and CaTi (CaTiAl2O6) models reveal substantial deviations from equilibrium with increasing ΔT, particularly in Al-rich zones. We postulate that this reflects slower diffusion of Al and Ti in the melt compared with Ca and Mg and recommend the concurrent application of these four models to evaluate equilibrium between clinopyroxene and melt, particularly for sector-zoned crystals. Thermobarometers calibrated with only isothermal–isobaric experiments closely reproduce experimental P–T at low ΔT, equivalent to natural phenocrysts cores and sector-zoned mantles. Models that also consider decompression experiments are most accurate at high ΔT and are therefore suitable for outermost phenocryst rims and groundmass microlites. Recent machine learning approaches reproduce P–T conditions across all ΔT conditions. Applying our experimental constraints to sector-zoned microphenocrysts and groundmass microlites erupted during the 1974 eccentric eruption at Mt. Etna, we highlight that both hourglass and prism sectors are suitable for thermobarometry, given that equilibrium is sufficiently tested for. The combination of DiHd, EnFs, CaTs and CaTi models identifies compositions closest to equilibrium with the bulk melt composition, and results in smaller differences in P–T calculated for hourglass and prism sectors compared with applying only DiHd and EnFs equilibrium models. This provides a framework to assess crystallisation conditions recorded by sector-zoned clinopyroxene crystals in mafic alkaline settings.

Mafic alkaline magmas, such as those feeding the persistent eruptive activity of Stromboli and Mt. Etna volcanoes in Italy, are dominated by the crystallization of plagioclase via cooling and degassing phenomena related to the dynamics of shallow crustal reservoirs and eruptive conduits. Because plagioclase textures and compositions are extremely sensitive to the changes of intensive variables in subvolcanic plumbing systems, the phenomenological variability of erupted crystals preserves detailed evidence of complex growth histories. From this point of view, we reappraise the textural maturation and compositional complexity of plagioclase by allying thermodynamic and kinetic principles to natural and experimental observations, with the purpose of drawing up guidelines for reconstructing magma dynamics in mafic alkaline volcanic settings. A multifaceted statistical method is adopted to parameterize the decay of crystal growth rate with increasing crystallization time, as relaxation kinetics prevails over melt supersaturation effects. This model parameterization is combined with the textural analysis of natural plagioclase crystals to quantify the residence time of phenocrysts in equilibrium with magmas at Stromboli and Mt. Etna and/or the timescale of rapid microlite growth during disequilibrium ascent of magmas within the conduit. The role played by temperature and melt-water content on plagioclase components and major cation substitution mechanisms is also evaluated under both isobaric-isothermal and decompression conditions. The emerging paradigm is that the influence of dissolved water on anorthite-albite exchange between plagioclase and melt is overwhelmingly mitigated by changes in temperature at conditions of P = 30–300 MPa, T = 1050–1150 °C, fO2 = NNO + 1.9-NNO + 2.3, and melt-H2O = 0.6–4.4 wt%. As a corollary, anorthite and albite melt activities are almost fully encapsulated in the variation of anhydrous melt components as the crystallization of plagioclase proceeds during magma cooling. Following this line of reasoning, we propose an integrated modeling approach to decipher complex zoning patterns in natural plagioclase phenocrysts from mafic alkaline eruptions. Key findings from our re-assessment of equilibrium, thermometric, and hygrometric models indicate that temperature and dissolved water can be iteratively estimated for different plagioclase textural patterns if crystals are sufficiently strongly zoned and probability-based criteria are applied to determine the maximum probability distribution from kernel density analysis.

In this study we parameterize the textural attributes of plagioclase phenocrysts and microlites from nineteen pyroclasts ejected during mild to violent explosions at Stromboli over a timespan of ∼18 years, from 2003 to 2021. By allying kinetic and crystal size distribution principles, we document that the morphological stability of large-sized, euhedral phenocrysts is superimposed on an internal textural heterogeneity due to growth-dissolution phenomena associated with the input rate of hot, H2O-rich recharge magmas rising from depth. As a result, the volumetric plagioclase proportion, dominant size, and number of phenocrysts per unit volume decrease from mild to violent explosions responding to a more efficient magma mixing process via sustained injections of mafic magmas into the shallow reservoir. On the other hand, the crystallization of anhedral plagioclase microlites is controlled by fast growth kinetics taking place in the uppermost part of the conduit during magma acceleration towards the surface. Under such highly dynamic crystallization conditions, the microlite number density closely depends on the increase of melt liquidus temperature via magma decompression and H2O exsolution. This mutualism allows to model the degassing rate and ascent velocity of magma under open-conduit flow regimes for the different eruptive styles, thereby supporting the idea that violent explosions at Stromboli are driven by sustained influxes of recharge magmas favoring strong acceleration (∼12–27 m/s), decompression (∼0.25–0.49 MPa/s), and H2O exsolution (∼0.005–0.01 wt%/s) before magma discharge at the vent.

Open-conduit basaltic volcanoes can be characterised by sudden large explosive events (paroxysms) that interrupt normal effusive and mild explosive activity. In June-August 2019, one major explosion and two paroxysms occurred at Stromboli volcano (Italy) within only 64 days. Here, via a multifaceted approach using clinopyroxene, we show arrival of mafic recharges up to a few days before the onset of these events and their effects on the eruption pattern at Stromboli, as a prime example of a persistently active, open-conduit basaltic volcano. Our data indicate a rejuvenated Stromboli plumbing system where the extant crystal mush is efficiently permeated by recharge magmas with minimum remobilisation promoting a direct linkage between the deeper and the shallow reservoirs that sustains the currently observed larger variability of eruptive behaviour. Our approach provides vital insights into magma dynamics and their effects on monitoring signals demonstrating the power of petrological studies in interpreting patterns of surficial activity.

In the period February–April 2021, seventeen energetic hours-long episodes of intense lava fountaining occurred at Mt. Etna, producing lava flows and ash plumes followed by heavy fallout. Clinopyroxene mesocrysts from these paroxysms show complex sector and concentric zoning patterns, with juxtaposition of Si-Mg-rich (Al-Ti-poor) and Si-Mg-poor (Al-Ti-rich) crystal layers. Clinopyroxene-based equilibrium thermobarometry and hygrometry define an overall crystallization path in the range of ~170–480 MPa, ~1060–1110 °C, and ~ 1.2–2.7 wt% H2O, with a main magma storage region estimated at depths of ~11–15 km. From this perspective, we observe that 2021 lava fountains were fed by hotter magmas of deeper origin with respect to those feeding 2011–2012 paroxysms. Zoning patterns of 2021 clinopyroxene mesocrysts formed in a vertically-extended plumbing system upon the effect of mixing phenomena and crystal recycling caused by recurrent inputs of fresh magmas into interconnected mushy reservoirs. Kinetic growth modeling constrains the formation of 2021 clinopyroxene mesocrysts over timescales of ~30–90 h and small degrees of undercooling ≤28 °C. Fesingle bondMg diffusion chronometry confirms that the time elapsed between the formation of clinopyroxene rim and magma eruption is utterly related to growth kinetics caused by pre-eruptive dynamic transfer of magma at crustal depths. Kinetic effects are exacerbated for clinopyroxene microlites/microcrysts forming at the syn-eruptive stage, when magma decompression, degassing, and cooling become more effective in the last 1.5 km below the vent of Mt. Etna. Kinetic growth modeling reveals that eruption dynamics within the conduit promote an exceptionally rapid disequilibrium growth of clinopyroxene microlites/microcrysts in only ~0.4–3.3 min upon large degrees of undercooling >60 °C. The resulting ascent velocity of 2021 magmas within the conduit is ~8–63 m/s, a factor of ~3 higher than the less energetic 2011–2012 paroxysms.

Intra-oceanic arcs are typically associated with intermediate (andesitic) cone volcanoes. However, caldera volcanoes may also form in these settings from very large eruptions, resulting in sudden changes to the magma reservoir. These reservoirs can then produce either semi-continuous or intermittent low-intensity volcanism between major caldera-producing or caldera-deepening eruptions, providing insights into the post-caldera evolution of the system. Hunga volcano (Kingdom of Tonga, Southwest Pacific) is a large mainly submarine edifice that produced a series of caldera-forming eruptions ~900 years ago. Since then, numerous smaller-scale subaerial and submarine eruptions occurred, the most recent forming new islands in 2009 and 2014/15. Pyroclastic deposits associated with these latest eruptions have identical (range ~ 0.1 wt% of all major oxides) andesitic composition that overlap with the primitive end of the slightly wider compositional range of the caldera-forming episodes. Texturally simple plagioclase, clinopyroxene and orthopyroxene phenocrysts in pre-, syn- and post-caldera pyroclasts point to a single shallow storage reservoir at 5–8 km depth. Lack of complex zonation indicates that this reservoir is constantly resupplied by low-flux inputs of basaltic andesite magma and is large enough that convective mixing rapidly homogenises new inputs. The reservoir feeds intermittent, low-intensity, post-caldera volcanism with constant andesite composition, driven possibly by magmatic overpressure and “leakage” of gas-rich magma pockets around the edges of the caldera. More primitive and compositionally variable basaltic andesites formed a lava-dominated edifice prior to the caldera-forming event. This suggests a causal link between magma supply dynamics and caldera priming relating to the maturing of the plumbing system and formation of a sustained subvolcanic andesite magma reservoir.

The hinterland of the Cenozoic Northern Apennines fold-and-thrust belt exposes the metamorphic roots of the chain, vestiges of the subduction-related tectono-metamorphic evolution that led to the buildup of the Alpine orogeny in the Mediterranean region. Like in other peri-Mediterranean belts, the tectono-metamorphic evolution of the Palaeozoic continental basement in the Apennines is still poorly constrained, hampering the full understanding of their Alpine orogenic evolution. We report the first comprehensive tectono-metamorphic study of the low-grade metasedimentary (metapsammite/metapelite) succession of the Monti Romani Complex (MRC) that formed after Palaeozoic protoliths and constitutes the southernmost exposure of the metamorphic domain of the Northern Apennines. By integrating fieldwork with microstructural studies, Raman spectroscopy on carbonaceous material and thermodynamic modelling, we show that the MRC preserves a D1/M1 Alpine tectono-metamorphic evolution developed under HP–LT conditions (~1.0–1.1 GPa at T ~ 400°C) during a non-coaxial, top-to-the-NE, crustal shortening regime. Evidence for HP–LT metamorphism is generally cryptic within the MRC, dominated by graphite-bearing assemblages with the infrequent blastesis of muscovite ± chlorite ± chloritoid ± paragonite parageneses, equilibrated under cold palaeo-geothermal conditions (~10°C/km). Results of this study allow extending to the MRC the signature of subduction zone metamorphism already documented in the hinterland of the Apennine orogen, providing further evidence of the syn-orogenic ductile exhumation of the HP units in the Apennine belt. Finally, we discuss the possible role of fluid-mediated changes in the reactive bulk rock composition on mineral blastesis during progress of regional deformation and metamorphism at low-grade conditions.

Sector-zoned clinopyroxene records kinetic effects imposed by variable degrees of magma undercooling, ΔT, and can be utilised to track the dynamics of magmatic systems. The partitioning of trace elements into sectors grown in different crystallographic orientations can be used as a proxy for ΔT. However, an experimental assessment of the relationship between trace element zoning and ΔT has been lacking to date. Here we present trace element data from a series of undercooling crystallisation experiments on a primitive trachybasalt from Mt. Etna (Italy), at conditions of crustal storage (400 MPa, NNO + 2), and ΔT ranging from 23 to 173 °C. Changes in ΔT were modulated by varying both resting and liquidus temperatures, the latter via the melt-H2O content of the experiments. The resting temperature was retained for 24 h to ensure the attainment of near-equilibrium conditions. High-resolution elemental mapping reveals the distribution of trace elements in individual clinopyroxene zones. Increasing ΔT drives a shift from polyhedral morphologies with Al-rich prism and Al-poor hourglass sectors (ΔT = 23–25 °C), to skeletal (ΔT = 75–123 °C) and dendritic (ΔT = 132–173 °C) crystals with Al-rich skeletons and Al-poor overgrowths. Aluminium-rich zones have higher concentrations of rare earth elements (REE) and high field strength elements (HFSE) than Al-poor zones across all investigated ΔT conditions, and overall, Al, REE and HFSE contents increase with ΔT. This indicates that tetrahedral aluminium (TAl) and associated charge-balancing mechanisms govern the incorporation of REE and HFSE within clinopyroxene. Lattice strain parameters for REE in the M2 site indicate the incorporation of light relative to heavy REE in clinopyroxene is controlled by competing effects between the strain-free partition coefficient, D0, and the optimum cation radius, r0. Critically, the middle and heavy REE switch from incompatible to compatible with increasing ΔT. Used to model fractional crystallisation, our data demonstrate that fractionation of clinopyroxene at low ΔT controls pre-eruptive melt evolution. Importantly, this indicates crystallisation of clinopyroxene in the deep portions of Mt. Etna’s plumbing system is not rapid and is unlikely to result in the early formation of dendrites. We develop a parameterisation of ΔT based on REE partitioning between experimental clinopyroxene and coexisting melt, which can be applied to sector-zoned augite crystallising from mafic alkaline magmas, to reconstruct dynamic processes and thermal pathways during magma transport and storage. Applied to sector-zoned clinopyroxene microphenocrysts and groundmass microcrysts from the 1974 eccentric eruption at Mt. Etna, our parameterisation tracks an increase in ΔT with magma ascent and eruption, following recharge of Cr-rich mafic magma at depth. Sector-zoned clinopyroxene can track ΔT variations leading to volcanism at Mt. Etna and could be applied to quantify magma dynamics in other active volcanoes.