Towards an understanding of disequilibrium dihedral angles in mafic rocks

The median dihedral angle at clinopyroxene-plagioclase-plagioclase junctions in mafic rocks, Θcpp, is generally lower than equilibrium (109˚ {plus minus} 2˚). Observation of a wide range of mafic bodies demonstrates that previous work on systematic variations of Θcpp is incorrect in several important respects. Firstly, the spatial distribution of plagioclase compositional zoning demonstrates that the final geometry of three-grain junctions, and hence Θcpp, is formed during solidification (the igneous process): sub-solidus textural modification in most dolerites and gabbros, previously thought to be the dominant control on Θcpp, is insignificant. Θcpp is governed by mass transport constraints, the inhibiting effects of small pore size on crystallization, and variation in relative growth rates of pyroxene and plagioclase. During rapid cooling, pyroxene preferentially fills wider pores while the narrower pores remain melt-filled, resulting in an initial value of Θcpp of 78˚, rather than 60˚ which would be expected if all melt-filled pores were filled with pyroxene. Lower cooling rates create a higher initial Θcpp due to changes in relative growth rates of the two minerals at the nascent three-grain junction. Low Θcpp (associated with cuspate clinopyroxene grains at triple junctions) can also be diagnostic of infiltration of previously melt-free rocks by late-stage evolved liquids (the metasomatic process). Modification of Θcpp by sub-solidus textural equilibration (the metamorphic process) is only important for fine-grained mafic rocks such as chilled margins and intra-plutonic chill zones. In coarse-grained gabbros from shallow crustal intrusions the metamorphic process occurs only in the centres of oikocrysts, associated with rounding of chadacrysts

Rapid pre-eruptive mush reorganisation and atmospheric volatile emissions from the 12.9 ka Laacher See eruption, determined using apatite

Magma is commonly thought to be stored as a crystal-rich mush within vertically extensive, crustal storage regions. A key unknown is how to remobilise and erupt such crystal-rich material, and whether the growth of gas bubbles within the mush could promote remobilisation. In order to investigate this, we need improved constraints on the timing of volatile saturation in magmas. The mineral apatite represents a potentially useful record of pre-eruptive magmatic volatiles, but data interpretation is complex because exchange reactions control the volatile partitioning. Model solutions are therefore non-unique. Here, we present a numerical forward modelling program with a sensitivity analysis function, which addresses non-uniqueness by identifying alternative sets of starting parameters that match a target compositional trend through a population of apatite crystals. The model is applied to a new dataset of volatiles in apatite from the 12.9 ka Laacher See eruption, Eifel volcanic region, Germany. The results indicate that the magma was initially strongly volatile-undersaturated and became saturated through progressive crystal fractionation. Apatite crystals are not in volatile or trace element equilibrium with their carrier melts, indicating dispersal of crystals into different chemical environments. Consideration of apatite diffusivities suggests that this reorganisation occurred shortly before eruption. Our modelling results also allow us to constrain directly the amount of pre-eruptive magmatic vapour emitted during the explosive eruption, highlighting the importance of considering the behaviour of halogens during magma storage. Overall, our approach confirms the value of measuring apatite volatile contents and highlights the potential of this method to provide quantitative constraints on magmatic evolution and storage conditions

Tracing Volatiles, Halogens, and Chalcophile Metals during Melt Evolution at the Tolbachik Monogenetic Field, Kamchatka

Melt storage and supply beneath arc volcanoes may be distributed between a central stratovolcano and wider fields of monogenetic cones, indicating complex shallow plumbing systems. However, the impact of such spatially variable magma storage conditions on volatile degassing and trace element geochemistry is unclear. This study explores magma generation and storage processes beneath the Tolbachik volcanic field, Kamchatka, Russia, in order to investigate the evolution of the magmatic volatile phase and, specifically, the strong enrichment of chalcophile metals (in particular, Cu) in this system. We present new geochemical data for a large suite of olivine- and clinopyroxene-hosted melt inclusions (and host phenocrysts) from five separate monogenetic cones within the Tolbachik volcanic field. These high-Al composition magmas likely reflect the homogenised fractionation products of primitive intermediate-Mg melt compositions, stored at shallow depths after significant fractional crystallisation. Boron isotope compositions and incompatible trace element ratios of the melt inclusions suggest a deeper plumbing system that is dominated by extensive fractional crystallisation and fed by melts derived from an isotopically homogeneous parental magma composition. Volatile components (H2O, CO2, S, Cl, F) show that magmas feeding different monogenetic cones had variable initial volatile contents and subsequently experienced different fluid-saturated storage conditions and degassing histories. We also show that melts supplying the Tolbachik volcanic field are strongly enriched in Cu compared with almost all other Kamchatka rocks, including samples from the Tolbachik central stratocones, and other volcanoes situated in close proximity in the Central Kamchatka Depression. The melt inclusions record Cu concentrations ≥450 μg/g at ca. 4–5 wt.% MgO, which can only be explained by bulk incompatible partitioning behaviour of Cu, i.e. evolution under sulphide-undersaturated conditions. We suggest that initial mantle melting in this region exhausted mantle sulphides, leading to sulphide undersaturated primitive melts. This sulphide-free model for the high-Al cone melts is further supported by S/Se and Cu/Ag values that overlap those of the primitive mantle and MORB array, with bulk rock Cu/Ag ratios also overlapping other with other global arc datasets for magma evolution prior to fractionation of a monosulfide solid solution. We therefore demonstrate that the combination of novel chalcophile metal analyses with trace element, isotopic, and volatile data is a powerful tool for deciphering complex magmatic evolution conditions across the entire volcanic field