A crystal mush perspective explains magma variability at la fossa volcano (Vulcano, Italy)

The eruptive products of the last 1000 years at La Fossa volcano on the island of Vulcano (Italy) are characterized by abrupt changes of chemical composition that span from latite to rhyolite. The wide variety of textural features of these products has given rise to several petrological models dealing with the mingling/mixing processes involving mafic-intermediate and rhyolitic magmas. In this paper, we use published whole-rock data for the erupted products of La Fossa and combine them in geochemical and thermodynamic modelling in order to provide new constrains for the interpretations of the dynamics of the active magmatic system. The obtained results allow us to pic-ture a polybaric plumbing system characterized by multiple magma reservoirs and related crystal mushes, formed from time to time during the differentiation of shoshonitic magmas, to produce latites, trachytes and rhyolites. The residing crystal mushes are periodically perturbated by new, fresh magma injections that, on one hand, induce the partial melting of the mush and, on the other hand, favor the extraction of highly differentiated interstitial melts. The subsequent mixing and mingling of mush-derived melts ultimately determine the formation of magmas erupted at La Fossa, whose textural and chemical features are otherwise not explained by simple assimilation and fractional crystallization models. In such a system, the compositional variability of the erupted products reflects the complexity of the physical and chemical interactions among recharging mag-mas and the crystal mushes

Direct quartz-coesite transformation in shocked porous sandstone from Kamil Crater (Egypt)

Coesite, a high-pressure silica polymorph (pressure 3–10 GPa, temperature <3000 K), is a diagnostic feature of shock metamorphism associated with impact cratering on quartz-bearing target rocks. It is preserved as a metastable phase in sedimentary target rocks that experienced peak pressures in excess of ~10 GPa, where it typically occurs as intergranular polycrystalline aggregates of microcrystals embedded in silica glass known as “symplectic regions.” The presence of coesite in the symplectic regions of rocks experiencing shock conditions beyond the limits of the coesite stability field is a controversial issue. Through a combined scanning and transmission electron microscopy and Raman spectroscopy study of shocked quartzarenites from the 45-m-diameter Kamil Crater (southwest Egypt), we show that coesite in symplectic regions forms through direct subsolidus transformation from quartz, in contrast with the prevailing hypothesis for crystalline targets. The quartz-to-coesite transformation takes place during localized shock-wave reverberation at the beginning of the pore collapse process. Complete pore collapse generates the high temperature regimes responsible for the subsequent production of the embedding silica melts, in part at the expense of the previously formed coesite. This work documents the role of pore collapse in producing localized pressure-temperature-time gradients in shocked porous targets, as predicted by numerical models in the literature

Clinopyroxene-liquid thermometers and barometers specific to alkaline differentiated magmas

We present new thermometers and barometers based on clinopyroxene-liquid equilibria specific to alkaline differentiated magmas. The new models were calibrated through the regression analyses of experimental datasets obtained by merging phase equilibria experiments from the literature with new experiments performed by using trachytic and phonolitic starting compositions. The regression strategy was twofold: (1) we have tested previous thermometric and barometric equations and recalibrated these models using the new datasets; (2) we have calibrated a new thermometer and a new barometer including only regression parameters that closely describe the compositional variability of the datasets. The new models yield more precise estimates than previous thermometers and barometers when used to predict temperatures and pressures of alkaline differentiated magmas. We have tested the reliability of the new equations by using clinopyroxene-liquid pairs from trachytes and phonolites erupted during major explosive eruptions at the Phlegrean Fields and Mt. Vesuvius (central Italy). The test yielded crystallization conditions comparable to those determined by means of melt and fluid inclusion analyses and phase equilibria studies; this validates the use of the proposed models for precise estimates of crystallization temperatures and pressures in differentiated alkaline magmas. Because these magmas feed some of the most voluminous, explosive, and threatening volcanic eruptions in the world, a better understanding of the environmental conditions of their reservoirs is mandatory and this is now possible with the new models provided here. © 2013 Springer-Verlag Berlin Heidelberg

CO2 bubble generation and migration during magma-carbonate interaction

We conducted quantitative textural analysis of vesicles in high temperature and pressure carbonate assimilation experiments (1200 °C, 0.5 GPa) to investigate CO2 generation and subsequent bubble migration from carbonate into magma. We employed Mt. Merapi (Indonesia) and Mt. Vesuvius (Italy) compositions as magmatic starting materials and present three experimental series using (1) a dry basaltic-andesite, (2) a hydrous basaltic-andesite (2 wt% H2O), and (3) a hydrous shoshonite (2 wt% H2O). The duration of the experiments was varied from 0 to 300 s, and carbonate assimilation produced a CO2-rich fluid and CaO-enriched melts in all cases. The rate of carbonate assimilation, however, changed as a function of melt viscosity, which affected the 2D vesicle number, vesicle volume, and vesicle size distribution within each experiment. Relatively low-viscosity melts (i.e. Vesuvius experiments) facilitated efficient removal of bubbles from the reaction site. This allowed carbonate assimilation to continue unhindered and large volumes of CO2 to beliberated, a scenario thought to fuel sustained CO2-driven eruptions at the surface. Conversely, at higher viscosity (i.e. Merapi experiments), bubble migration became progressively inhibited and bubble concentration at the reaction site caused localised volatile over-pressure that can eventually trigger short-lived explosive outbursts. Melt viscosity therefore exerts a fundamental control on carbonate assimilation rates and, by consequence, the style of CO2-fuelled eruptions

Major explosive activity in the Monti Sabatini Volcanic District(central Italy) over the 800-390ka interval: Geochronological-geochemical overview and tephrostratigraphic implications

A review of the existing chronological, stratigraphic and chemo-petrologic data of the major eruptive units from the early phase of activity (800-390ka) in the Monti Sabatini Volcanic District (MSVD), belonging to the ultra-potassic magmatic region of central Italy, is presented along with new radioisotopic age determinations and geochemical analyses. Through the combined use of electron microprobe glass compositions, selected trace-element compositions, and single-crystal 40Ar/39Ar age determinations, we provide a new chrono- and chemo-stratigraphic classification of the products emplaced in the 800-390ka time interval. Besides giving insights on the petrologic evolution of the Roman Comagmatic Region, the large dataset provides fundamental information that is applicable to tephrostratigraphic studies in the wide region encompassing the Tyrrhenian Sea margin to the Adriatic Sea basin. Distal tephras from this volcanic activity also act as important geochronologic markers for the coastal sedimentary successions deposited in response to glacio-eustatic fluctuations, as well as for successions in the Quaternary tectonic basins of the Central and Southern Apennines. An innovative approach based on the use of discrimination diagrams of Zr/Y vs Nb/Y ratios for fingerprinting altered volcanic rocks - recently developed and successfully employed in archaeometric studies - is here combined to the glass compositions for classifying the MSVD deposits and tested on two distal tephra layers, showing its potentiality for tephrostratigraphic correlation. © 2014 Elsevier Ltd

Decarbonation and thermal microcracking under magmatic P-T-fCO2 conditions: the role of skarn substrata in promoting volcanic instability

We present a systematic study on the influence of pressure (0.1-600 MPa), temperature (750- 1200oC), carbon dioxide fugacity (logfCO2 = -4.41 to 3.60) and time (2-12 hr) on the chemical and physical properties of carbonate rock. Our experiments aim to reproduce the conditions at the periphery of magma chamber where carbonate host rock is influenced by, but not readily assimilated by, magma. This permits the investigation of the natural conditions at which circulating fluids/gases promote infiltration reactions typical of metasomatic skarns that can involve large volumes of subvolcanic carbonate basements. Results show that, providing that carbon dioxide is retained in the pore space, decarbonation does not proceed at any magmatic pressure and temperature. However, when the carbon dioxide is free to escape, decarbonation can occur rapidly and is not hindered by a low initial porosity or permeability. Together with carbon dioxide and lime, portlandite, a mineral commonly found in voluminous metasomatic skarns, readily forms during carbonate decomposition. Post-experimental analyses highlight that thermal microcracking, a result of the highly anisotropic thermal expansion of calcite, exerts a greater influence on rock physical properties (porosity, ultrasonic wave velocities and elastic moduli) than decarbonation. Our data suggest that this will be especially true at the margins of dykes or magma bodies, where temperatures can reach up to 1200oC. However, rock compressive strength is significantly reduced by both thermal cracking and decarbonation, explained by the relative weakness of lime + portlandite compared to calcite, and an increase in grain size with increasing temperature. Metasomatic skarns, whose petrogenetic reactions may involve a few tens of cubic kilometres, could therefore represent an important source of volcanic instability. © The Authors 2013 Published by Oxford University Press on behalf of The Royal Astronomical Society

CO2 bubble generation and migration during magma–carbonate interaction

We conducted quantitative textural analysis of vesicles in high temperature and pressure carbonate assimilation experiments (1200 °C, 0.5 GPa) to investigate CO2 generation and subsequent bubble migration from carbonate into magma. We employed Mt. Merapi (Indonesia) and Mt. Vesuvius (Italy) compositions as magmatic starting materials and present three experimental series using (1) a dry basaltic-andesite, (2) a hydrous basaltic-andesite (2 wt% H2O), and (3) a hydrous shoshonite (2 wt% H2O). The duration of the experiments was varied from 0 to 300 s, and carbonate assimilation produced a CO2-rich fluid and CaO-enriched melts in all cases. The rate of carbonate assimilation, however, changed as a function of melt viscosity, which affected the 2D vesicle number, vesicle volume, and vesicle size distribution within each experiment. Relatively low-viscosity melts (i.e. Vesuvius experiments) facilitated efficient removal of bubbles from the reaction site. This allowed carbonate assimilation to continue unhindered and large volumes of CO2 to be liberated, a scenario thought to fuel sustained CO2-driven eruptions at the surface. Conversely, at higher viscosity (i.e. Merapi experiments), bubble migration became progressively inhibited and bubble concentration at the reaction site caused localised volatile over-pressure that can eventually trigger short-lived explosive outbursts. Melt viscosity therefore exerts a fundamental control on carbonate assimilation rates and, by consequence, the style of CO2-fuelled eruptions

Effect of undercooling on clinopyroxene crystallization in a high K basalt. Implications for magma dynamics at Stromboli volcano

We present undercooling (ΔT) 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 (ΔTanh = 10–150 ◦C) and hydrous (ΔThyd = 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 ΔTanh = 10 ◦C and dominates the phase assemblage as the degree of undercooling increases. Conversely, clinopyroxene and spinel co-saturate the melt at ΔThyd = 25 ◦C, followed by the subordinate formation of plagioclase. At ΔTanh/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 ΔTanh/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 ΔTanh/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 ΔThyd are also more enriched in TAl and M1Ti and depleted in TSi and M1Mg than those growing at ΔTanh. 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

Amphibole and apatite insights into the evolution and mass balance of Cl and S in magmas associated with porphyry copper deposits

Chlorine and sulfur are of paramount importance for supporting the transport and deposition of ore metals at magmatic–hydrothermal systems such as the Coroccohuayco Fe–Cu–Au porphyry–skarn deposit, Peru. Here, we used recent partitioning models to determine the Cl and S concentration of the melts from the Coroccohuayco magmatic suite using apatite and amphibole chemical analyses. The pre-mineralization gabbrodiorite complex hosts S-poor apatite, while the syn- and post-ore dacitic porphyries host S-rich apatite. Our apatite data on the Coroccohuayco magmatic suite are consistent with an increasing oxygen fugacity (from the gabbrodiorite complex to the porphyries) causing the dominant sulfur species to shift from S2− to S6+ at upper crustal pressure where the magmas were emplaced. We suggest that this change in sulfur speciation could have favored S degassing, rather than its sequestration in magmatic sulfides. Using available partitioning models for apatite from the porphyries, pre-degassing S melt concentration was 20–200 ppm. Estimates of absolute magmatic Cl concentrations using amphibole and apatite gave highly contrasting results. Cl melt concentrations obtained from apatite (0.60 wt% for the gabbrodiorite complex; 0.2–0.3 wt% for the porphyries) seems much more reasonable than those obtained from amphibole which are very low (0.37 wt% for the gabbrodiorite complex; 0.10 wt% for the porphyries). In turn, relative variations of the Cl melt concentrations obtained from amphibole during magma cooling are compatible with previous petrological constraints on the Coroccohuayco magmatic suite. This confirms that the gabbrodioritic magma was initially fluid undersaturated upon emplacement, and that magmatic fluid exsolution of the gabbrodiorite and the pluton rooting the porphyry stocks and dikes were emplaced and degassed at 100–200 MPa. Finally, mass balance constraints on S, Cu and Cl were used to estimate the minimum volume of magma required to form the Coroccohuayco deposit. These three estimates are remarkably consistent among each other (ca. 100 km3) and suggest that the Cl melt concentration is at least as critical as that of Cu and S to form an economic mineralization