Bubble and crystal nucleation and growth dynamics play a vital function in determining the eruptive behaviour of a magma. Investigating the initial stages of bubble nucleation and crystallization processes, including their rate and relative timing, can thus give us insight into the eruption parameters of magmas including their rheology. Although many experiments and numerical simulations of decompression-induced vesicle nucleation in magmas have been carried out, the mechanisms of bubble nucleation remain poorly understood. It is widely accepted that there are two ways bubbles can form: either by homogeneous nucleation within a melt, or by heterogeneous nucleation on a surface, interface, or particle. It has been tentatively suggested that what had been interpreted as homogeneous nucleation in magmas was instead heterogeneous nucleation on the surface of elusive nano- or micro-scale crystals present throughout the melt. Herein, we have conducted an experiment whereby bubble nucleation is induced in a synthetic andesitic glass sample using radiation damage from a focused ion beam (FIB) to investigate the initial stages of bubble nucleation. Scanning transmission electron microscopy, electron energy-loss spectroscopy and atom probe tomography (APT) data reveal sub-nanometer scale chemical heterogeneities in the form of Fe-, Na-, and/or Ca-rich clusters at the bubble-glass interface of the newly created bubbles. Comparatively, specimens prepared by cryogenic FIB, in which bubble nucleation is suppressed, are without bubbles; however, APT data shows similar chemical heterogeneities suggesting these clusters existed within the synthetic glass prior to bubble formation. Based on these observations, our data demonstrate the existence of nanoscale chemical heterogeneities within a synthetic silicate glass and at bubble-glass interfaces. Although our experiments do not replicate the conditions of natural processes, our results contribute to the hypothesis that previously described homogeneous nucleation may be re-interpreted as a variety of heterogeneous nucleation. These findings highlight the need to revise the commonly used definition of homogeneous nucleation among magma scientists.

The mutual affinity between bubbles and oxide crystals (especially magnetite) is well established and their tendency to remain in contact once they become connected (either by nucleation of one upon the other, or by attachment) has led to models of oxide transport via bubbles in natural melts. However, despite the widespread acceptance of bubble–oxide association, there is little direct textural evidence for these processes. We present results from a series of decompression experiments on andesitic melts, during which aggregates of bubbles and oxides formed because of hydrogen loss through the capsule walls causing oxidation of the melt. Experimental charges were imaged using 3D X-ray computed tomography that revealed complex bubble + oxide aggregates, with small oxide crystals coating part of the outer bubble surfaces in a shell-like morphology. These shells have smooth inner and rugose outer surfaces. Sometimes, additional concentric shells or partial shells can be found around bubbles, in the glass between the bubble wall and another shell. We quantified the volumes of bubbles and oxides and the oxides’ compositions. We measured the surface area where the bubbles and oxides are in contact, thus quantifying their interface in 3D, and used these measurements to investigate the process of oxide shell formation. The complexity of the oxide textures when studied in 3D reveals a range of bubble–oxide interactions, from continuous generation, detachment and disintegration. These processes carry important implications on why such textures seem to have a low preservation potential in natural environments. Nevertheless, we have found natural samples that resemble our experimental results in a range of rock compositions from different geological environments that could have formed either due to rapid oxidation via the fluid phase or by bubbles harvesting different crystals.

The nucleation, growth and attachment/detachment of gas bubbles on crystals in silicate melts is one of the key drivers of volcanic eruptions and can greatly influence their explosivity. Formerly, oxides were considered the best candidates for heterogeneous bubble nucleation, but recent studies showed that silicate crystals can also be bubble nucleation sites at 1 atmosphere (atm). This study examines whether bubbles can nucleate on plagioclase crystal surfaces during decompression, which is a more common natural situation than 1 atm degassing. Experimental samples were synthesised from andesitic rock powder, H2O and plagioclase seed crystals, and melted and decompressed in a piston-cylinder apparatus. The products were imaged with 3D X-ray computed tomography. Due to partial melting, the plagioclase crystals developed sieve rims and rough crystal-melt interfaces. All plagioclase crystals in all samples were covered with bubbles. Bubble size distribution comparisons between bubbles in contact with plagioclase and bubbles in the melt, show that bubbles belong to two populations, generated by two different events, one of which is heterogeneous nucleation on plagioclase crystal surfaces and the other is homogeneous nucleation within the melt, the latter potentially accompanied by heterogeneous nucleation on oxide microlite surfaces. The calculated attachment force between the bubbles and the plagioclase surface is stronger than the detachment force; hence, such bubbles would remain attached during crystal movements. In our experiments, the net buoyancy of the bubble-crystal aggregates indicates that they could sink in an andesitic melt. Our findings highlight the need to reconsider the role of plagioclase crystals in magmatic degassing and shows interesting possibilities for magma mixing-triggered degassing. (C) 2019 Elsevier B.V. All rights reserved.

Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location – either homogeneously within the melt or heterogeneously at the interface between crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25–0.5wt% H2O and seed silicate crystals were heated at 1atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.

The distribution of platinum-group elements (PGE) within zoned magmatic ore bodies has been extensively studied and appears to be controlled by the partitioning behavior of the PGE during fractional crystallization of magmatic sulfide liquids. However, other chalcophile elements, especially TABS (Te, As, Bi, Sb, and Sn) have been neglected despite their critical role in forming platinum-group minerals (PGM). TABS are volatile trace elements that are considered to be mobile so investigating their primary distribution may be challenging in magmatic ore bodies that have been somewhat altered. Magmatic sulfide ore bodies from the Noril'sk-Talnakh mining district (polar Siberia, Russia) offer an exceptional opportunity to investigate the behavior of TABS during fractional crystallization of sulfide liquids and PGM formation as the primary features of the ore bodies have been relatively well preserved. In this study, new petrographic (2D and 3D) and whole-rock geochemical data from Cu-poor to Cu-rich sulfide ores of the Noril'sk-Talnakh mining district are integrated with published data to consider the role of fractional crystallization in generating mineralogical and geochemical variations across the different ore types (disseminated to massive). Despite textural variations in Cu-rich massive sulfides (lenses, veins, and breccias), these sulfides have similar chemical compositions, which suggests that Cu-rich veins and breccias formed from fractionated sulfide liquids that were injected into the surrounding rocks. Numerical modeling using the median disseminated sulfide composition as the initial sulfide liquid composition and recent D-MSS/liq and D-ISS/liq predicts the compositional variations observed in the massive sulfides, especially in terms of Pt, Pd, and TABS. Therefore, distribution of these elements in the massive sulfides was likely controlled by their partitioning behavior during sulfide liquid fractional crystallization, prior to PGM formation. Our observations indicate that in the Cu-poor massive sulfides the PGM formed as the result of exsolution from sulfide minerals whereas in the Cu-rich massive sulfides the PGM formed by crystallization from late-stage fractionated sulfide liquids. We suggest that the significant amount of Sn-bearing PGM may be related to crustal contamination from granodiorite, whereas As, Bi, Te, and Sb were likely added to the magma along with S from sedimentary rocks. Large PGM that are scarce and randomly distributed may account for most of the whole-rock Pt budget. Based on our results, we propose a holistic genetic model for the formation of the magmatic sulfide ore bodies of the Noril'sk-Talnakh mining district. (C) 2017 Elsevier B.V. All rights reserved.