Chapter 1.INTRODUCTION TO OXYGEN FUGACITY AND ITS PETROLOGIC IMPORTANCE

Silicic magma systems are of great scientific interest and societal importance owing to their role in the evolution of the crust and the hazards posed by volcanic eruptions. MELTS is a powerful and widely used tool to study the evolution of magmatic systems over a wide spectrum of compositions and conditions. However, the current calibration of MELTS fails to correctly predict the position of the quartz þ feldspar saturation surface in temperature, pressure and composition space, making it unsuitable to study silicic systems. We create a modified calibration of MELTS optimized for silicic systems, dubbed rhyolite-MELTS, using early erupted Bishop pumice as a reference. Small adjustments to the calorimetrically determined enthalpy of formation of quartz and of the potassium end-member of alkali feldspar in the MELTS calibration lead to much improved predictions of the quartz þ feldspar saturation surface as a function of pressure. Application of rhyolite-MELTS to the Highland Range Volcanic Sequence (Nevada), the Peach Spring Tuff (Arizona^Nevada^California), and the late-erupted Bishop Tuff (California), using compositions that vary from trachydacite to high-silica rhyolite, shows that the calibration is appropriate for a variety of fluid-bearing silicic systems. Some key observations include the following. (1) The simulated evolutionary paths are consistent with petrographic observations and glass compositions; further work is needed to compare predicted and observed mineral compositions. (2) The nearly invariant nature of silicic magmas is well captured by rhyolite-MELTS; unusual behavior is observed after extensive pseudo-invariant crystallization, suggesting that the new calibration works best for relatively small (i.e.550 wt %) crystallization intervals, comparable with what is observed in volcanic rocks. (3) Our success with rhyolite-MELTS shows that water-bearing systems in which hydrous phases do not play a critical role can be appropriately handled; simulations are sensitive to initial water concentration, and although only a pure-H2O fluid is modeled, suitable amounts of water can be added or subtracted to mimic the effect of CO2 in fluid solubility. Our continuing work on natural systems shows that rhyolite-MELTS is very useful in constraining crystallization conditions, and is particularly well suited to explore the eruptive potential of silicic magmas. We show that constraints placed by rhyoliteMELTS simulations using late-erupted Bishop Tuff whole-rock and melt inclusion compositions are inconsistent with a vertically stratified magma body.

Rhyolite-MELTS: A Modified Calibration of MELTS Optimized for Silica-Rich, Fluid-Bearing Magmatic Systems

INGV-DPC Project V3_1 Colli Albani 
MIUR ‘Caratteristiche vulcanologiche e geomeccaniche 
dei prodotti recenti dei Colli Albani’.

Carbonate assimilation in open magmatic systems: the role of melt-bearing skarns and cumulate-forming processes

https://hal.archives-ouvertes.fr/hal-02324339/document

Complex conductivity of volcanic rocks and the geophysical mapping of alteration in volcanoes

Contrasting styles of post-caldera volcanism along the Main Ethiopian Rift: Implications for contemporary volcanic hazards

Furnas is one of three active central volcanoes on Sao Miguel Island, Azores, and is considered to be one of the most hazardous in the archipelago. In this study, the pre-eruptive magma plumbing system of the 10 young (<5 ka), intra-caldera, sub-Plinian, trachytic eruptions of the Upper Furnas Group (UFG) is investigated via whole rock major and trace element geochemistry, mineral chemistry, thermobarometry, and petrogenetic modelling. The main aim of this work is to elucidate the petrogenesis of the Furnas trachytes, constrain the P–T–fO2 conditions under which they evolve, and investigate the temporal evolution of the magma plumbing system. Results indicate that the trachytes are derived predominantly from extended fractional crystallisation of alkali basalt parental magmas, at depths between ~3 and 4 km. This is considered to take place in a density-stratified reservoir, with alkali basalt magmas at the base and hydrous trachytes forming an upper cap or cupola. The presence of this reservoir at shallow crustal depths beneath the caldera likely inhibits the ascent and subsequent eruption of mafic magmas, generating a compositional Daly Gap. Rare syenitic ejecta represent in situ crystallisation of trachytic magmas in the thermal boundary zone at the top of the reservoir. Trachytic enclaves within these syenites, in addition to banded pumices and ubiquitous clinopyroxene antecrysts in the UFG pumice falls, provide evidence for mingling/mixing processes within the magmatic system. Despite relatively uniform major element compositions, systematic trace element variations within individual eruptions highlight the importance of fractional crystallisation during late-stage evolution of the trachytes. This is facilitated by the accumulation of water and the development of mild peralkalinity, which contribute to low pre-eruptive melt viscosities and efficient crystal settling. Compositional zoning patterns between individual eruptions cannot be accounted for by periodic tapping of a single magma batch undergoing fractional crystallisation. Instead, up to four individual cycles are recognised, in which a zoned cap of eruptible trachytic magma, formed at the top of the reservoir, was erupted in one or more eruptions and was re-established via intermittent replenishment and subsequent fractional crystallisation.

/pdf/temporal-evolution-of-a-post-caldera-mildly-peralkaline-2f3ki1nbi0.pdf

Temporal evolution of a post-caldera, mildly peralkaline magmatic system: Furnas volcano, São Miguel, Azores

Interaction between magma and crustal carbonate at active arc volcanoes has recently been proposed as a source of atmospheric CO2, in addition to CO2 released from the mantle and subducted oceanic crust. However, quantitative constraints on efficiency and timing of these processes are poorly established. Here, we present the first in situ carbon and oxygen isotope data of texturally distinct calcite in calc-silicate xenoliths from arc volcanics in a case study from Merapi volcano (Indonesia). Textures and C-O isotopic data provide unique evidence for decarbonation, magma-fluid interaction, and the generation of carbonate melts. We report extremely light δ13CPDB values down to -29.3‰ which are among the lowest reported in magmatic systems so far. Combined with the general paucity of relict calcite, these extremely low values demonstrate highly efficient remobilisation of crustal CO2 over geologically short timescales of thousands of years or less. This rapid release of large volumes of crustal CO2 may impact global carbon cycling.

/pdf/crustal-co2-contribution-to-subduction-zone-degassing-52aqvj7dh1.pdf

Crustal CO2 contribution to subduction zone degassing recorded through calc-silicate xenoliths in arc lavas

\n Magma–carbonate interaction is an increasingly recognized process occurring at active volcanoes worldwide, with implications for the magmatic evolution of the host volcanic systems, their eruptive behaviour, volcanic CO2 budgets, and economic mineralization. Abundant calc-silicate skarn xenoliths are found at Merapi volcano, Indonesia. We identify two distinct xenolith types: magmatic skarn xenoliths, which contain evidence of formation within the magma; and exoskarn xenoliths, which more likely represent fragments of crystalline metamorphosed wall rocks. The magmatic skarn xenoliths comprise distinct compositional and mineralogical zones with abundant Ca-enriched glass (up to 10 wt % relative to lava groundmass), mineralogically dominated by clinopyroxene (En15-43Fs14-36Wo41-51) + plagioclase (An37-100) ± magnetite in the outer zones towards the lava contact, and by wollastonite ± clinopyroxene (En17-38Fs8-34Wo49-59) ± plagioclase (An46-100) ± garnet (Grs0-65Adr24-75Sch0-76) ± quartz in the xenolith cores. These zones are controlled by Ca transfer from the limestone protolith to the magma and by the transfer of magma-derived elements in the opposite direction. In contrast, the exoskarn xenoliths are unzoned and essentially glass-free, representing equilibration at sub-solidus conditions. The major mineral assemblage in the exoskarn xenoliths is wollastonite + garnet (Grs73-97Adr3-24) + Ca-Al-rich clinopyroxene (CaTs0-38) + anorthite ± quartz, with variable amounts of either quartz or melilite (Geh42-91) + spinel. Thermobarometric calculations, fluid-inclusion microthermometry and newly calibrated oxybarometry based on Fe3+/ΣFe in clinopyroxene indicate magmatic skarn xenolith formation conditions of ∼850 ± 45°C, < 100 MPa and at an oxygen fugacity between the NNO (nickel–nickel oxide) and HM (hematite-magnetite) buffer. The exoskarn xenoliths, in turn, formed at 510–910°C under oxygen-fugacity conditions between NNO and air. These high oxygen fugacities are likely imposed by the large volumes of CO2 liberated from the carbonate. Halogen- and sulphur-rich mineral phases in the xenoliths testify to infiltration by a magmatic brine. In some xenoliths, this is associated with the precipitation of copper-bearing mineral phases by sulphur dissociation into sulphide and sulphate, indicating potential mineralization in the skarn system below Merapi. The compositions of many xenolith clinopyroxene and plagioclase crystals overlap with that of magmatic minerals, suggesting that the crystal cargo in Merapi magmas may contain a larger proportion of skarn-derived xenocrysts than previously recognized. Assessment of xenolith formation timescales demonstrates that magma–carbonate interaction and associated CO2 release could affect eruption intensity, as recently suggested for Merapi and similar carbonate-hosted volcanoes elsewhere.

/pdf/magmatic-and-metasomatic-effects-of-magma-carbonate-3pzczj3y9m.pdf

Sean Whitley

Papers

Temporal evolution of a post-caldera, mildly peralkaline magmatic system: Furnas volcano, São Miguel, Azores

Crustal CO2 contribution to subduction zone degassing recorded through calc-silicate xenoliths in arc lavas

Magmatic and Metasomatic Effects of Magma–Carbonate Interaction Recorded in Calc-silicate Xenoliths from Merapi Volcano (Indonesia)