Formation of surficial sulfate– and halide–bearing salts by syn–eruptive ash–gas interactions is known to occur during volcanic eruptions. For reactions between aluminosilicates and the gas SO2, at high temperature regimes (T≥ 600 °C), the controlling mechanism is the outward chemical diffusion of alkalis and alkaline earth metals, predominantly Ca2+, that result in sulfate salt formation, mostly CaSO4, on glass surfaces. However, most of the experimental research has been conducted for SO2–reactions with pure crystal–free, aluminosilicate glass, to simplify the complexities of crystal–bearing systems. Here, we tested high temperature SO2–reactions using particles of a rhyolitic, crystal–bearing dome material from a 2013 eruption of Santiaguito volcano (Guatemala), by exposing 2 g of particles to 25 sccm of SO2; at 600–800 °C, for 5–60 min each time. We then compare our results with those of previous studies using pure glass particles, aiming to determine the influence of crystal fraction and type on the occurrence and efficiency of gas–ash reactions. We conducted chemical and microscopic analysis of pre– and post–treated samples and observed that diffusion of Ca2+ is reduced in crystal–bearing samples relative to crystal–free samples at the same conditions. The rate of slow–down of the diffusion process appears to be dependent on the crystal volume fraction, providing a mechanism to account for this effect a priori. SEM images also showed that surface componentry strongly affects presence of CaSO4, as salts appear to be absent on specific surface spots corresponding to crystal phases. Our results illustrate the need for ash-gas reaction studies to further consider both the effect of bulk– and surface–componentry, in order to more accurately assess syn-eruptive gas uptake by ash.

Energetic ash-producing volcanic eruptions are driven by the diffusive and decompressive growth of bubbles (mostly water) during ascent in a magma conduit. The spatial distribution of bubble nucleation sites is one of the primary controls on ash-forming fragmentation. However, the initial formation of bubbles in a supersaturated magma is problematical, especially for homogeneous nucleation. Excessive surface tension pressure should preclude the existence of small bubbles, because exsolved water is driven back into the melt. This is the “tiny bubble paradox.” We suggest that—under special circumstances—the tiny bubble paradox may be circumvented by spinodal decomposition, a process in which uphill diffusion enables spontaneous unmixing of phases to reduce the free energy of the system. As spinodal decomposition progresses, three dimensional, quasi-spherical, zones of water-rich magma develop. These zones are characterized by an increasingly high concentration of dissolved water at the centers and reducing concentration at the margins. Bubbles are born when the concentration of water in the interior of the water-rich zones goes to 100% and the concentration of melt goes to zero. The small, nascent, bubbles that emerge will be buffered from melt by water-rich shells with increasing melt concentration away from newly formed bubbles. This diffuse concentration gradient of water means that there is no surface, per se, for surface tension to arise. This is the crux of the solution of the tiny bubble paradox. Particle morphology may be used to distinguish ash with spinodal origins from ash associated with typical (metastable) bubble nucleation. Spinodal decomposition occurs at a wavelength determined by the pressure, temperature, and viscosity of the magmatic system. This wavelength should create bubbles of uniform size and bubble walls of equal strength in a fragmenting magmatic foam, leading to sharply mono-modal vesicle and ash particle size distributions. Classical bubble nucleation should create more-variable bubble sizes and bubble wall strengths, leading to a broader particle size distribution. Better understanding the mechanism of bubble formation in magmatic systems will, in turn, enable better understanding of hazardous, explosive, eruptions.