Olivine-hosted melt inclusions are commonly used to determine pre-eruptive storage conditions. However, this approach relies on the assumption that co-erupted olivines have a simple association with their carrier melts. We show that primitive olivine crystal cargoes and their melt inclusions display a high degree of geochemical disequilibrium with their carrier melts at Kīlauea Volcano, Hawai’i. Within a given eruption, melt inclusions trapped in primitive olivine crystals exhibit compositional diversity exceeding that in erupted lava compositions since 1790 CE. This demonstrates that erupting liquids scavenge crystal cargoes from mush piles accumulating diverse melt inclusion populations over timescales of centuries or longer. Entrainment of hot primitive olivines into cooler, evolved carrier melts drives post-entrapment crystallization and sequestration of CO2 into vapour bubbles, producing spurious barometric estimates. While scavenged melt inclusion records may not be suitable for the investigation of eruption-specific processes, they record timescales of crystal storage and remobilization within magmatic mush piles.

The 2018 lower East Rift Zone (LERZ) eruption and the accompanying collapse of the summit caldera marked the most destructive episode of activity at Kı̄lauea Volcano in the last 200 years. The eruption was extremely well‐monitored, with extensive real‐time lava sampling as well as continuous geodetic data capturing the caldera collapse. This multiparameter data set provides an exceptional opportunity to determine the reservoir geometry and magma transport paths supplying Kı̄lauea’s LERZ. The forsterite contents of olivine crystals, together with the degree of major element disequilibrium with carrier melts, indicates that two distinct crystal populations were erupted from Fissure 8 (termed high‐ and low‐Fo). Melt inclusion entrapment pressures reveal that low‐Fo olivines (close to equilibrium with their carrier melts) crystallized within the Halema’uma’u reservoir (∼2‐km depth), while many high‐Fo olivines (>Fo81.5; far from equilibrium with their carrier melts) crystallized within the South Caldera reservoir (∼3–5‐km depth). Melt inclusions in high‐Fo olivines experienced extensive post‐entrapment crystallization following their incorporation into cooler, more evolved melts. This favored the growth of a CO2‐rich vapor bubble, containing up to 99% of the total melt inclusion CO2 budget (median = 93%). If this CO2‐rich bubble is not accounted for, entrapment depths are significantly underestimated. Conversely, reconstructions using equation of state methods rather than direct measurements of vapor bubbles overestimate entrapment depths. Overall, we show that direct measurements of melts and vapor bubbles by secondary‐ion mass spectrometry and Raman spectroscopy, combined with a suitable H2O‐CO2 solubility model, is a powerful tool to identify the magma storage reservoirs supplying volcanic eruptions.

Understanding the solubility and degassing of volatiles in silicate melts is a crucial component of modeling volcanic systems. As dissolved components, volatiles (primarily 2 H E O and 2 CO E) affect magma viscosity, rheology, and crystal growth. In addition, due to the strong dependence of volatile solubility on pressure, measured volatile concentrations in preserved high-pressure melts (i.e., melt inclusions: liquid magma trapped within crystals at high pressure, then brought to the surface during an eruption) can be used to determine preeruptive magmatic storage pressures, and thus depths. Importantly, volatile exsolution-driven overpressure of a magmatic system is likely the trigger of many explosive volcanic eruptions (Blake, 1984; Stock IACOVINO ET AL.

Chalcophile element concentrations in melt inclusions and matrix glasses may be used to investigate low pressure degassing processes, as well as sulfide saturation during crustal fractionation, and mantle melting. Erupted products from Kīlauea Volcano, Hawaii record three stages of sulfide saturation (in the mantle, crust, and within lava lakes), separated by episodes of sulfide resorption (i.e., sulfide undersaturation) during ascent through the thick Hawaiian lithosphere, and during syn-eruptive degassing. The presence of residual sulfides in the mantle source throughout the melting interval accounts for the high S concentrations of Kīlauean primary melts (1387-1600 ppm). Residual sulfides retain chalcophile elements during melting, decoupling the variability of these elements in high MgO melts from that of lithophile elements. Decompression associated with magma ascent through the thick Hawaiian lithosphere drives an increase in the sulfide concentration at sulfide saturation (SCSS 2−), resulting in shallow storage reservoirs (∼1-5 km depth) being supplied with sulfide-undersaturated melts. A drop in temperature, coupled with major element changes during the fractionation of olivine, causes the SCSS 2− to decrease. Combined with an increase in melt S contents during fractionation, this initiates a second stage of sulfide saturation at relatively high MgO contents (∼12 wt%). Syn-eruptive degassing of S drives the resorption of sulfides in contact with the carrier liquid. The covariance structure of Cu, MgO and Ni contents in melt inclusions and matrix glasses indicates that the dissolution of sulfides effectively liberates sulfide-hosted Cu and Ni back into the melt, rather than the vapour phase. The contrasting behaviour of Cu, Ni, Se and S during sulfide resorption indicates that the chalcophile element signature of the Kīlauean plume is largely controlled by silicate melt-vapour partitioning, rather than sulfide-vapour partitioning. The participation of dense sulfide liquids in shallow degassing processes may result from their direct attachment to buoyant vapour bubbles, or olivine crystals which were remobilized prior to eruption. Sulfide resorption obscures the textural and chemical record of sulfide saturation in matrix glasses, but not in melt inclusions, which are isolated from this late-stage release of chalcophile elements. The partitioning of S between the dissolving sulfide, melt and the vapour phase accounts for approximately 20% of the total S release into the atmosphere.

Thermodynamics has been fundamental to the interpretation of geologic data and modeling of geologic systems for decades. However, more recent advancements in computational capabilities and a marked increase in researchers’ accessibility to computing tools has outpaced the functionality and extensibility of currently available modeling tools. Here we present VESIcal (Volatile Equilibria and Saturation Identification calculator): the first comprehensive modeling tool for H2 O, CO2 , and mixed (H2 O-CO2 ) solubility in silicate melts that: a) allows users access to seven of the most popular models, plus easy inter-comparison between models; b) provides universal functionality for all models (e.g., functions for calculating saturation pressures, degassing paths, etc.); c) can process large datasets (1,000’s of samples) automatically; d) can output computed data into an excel spreadsheet for simple post-modeling analysis; e) integrates advanced plotting capabilities directly within the tool; and f) provides all of these within the framework of a python library, making the tool extensible by the user and allowing any of the model functions to be incorporated into any other code capable of calling python. The tool is presented within this manuscript, which is a Jupyter notebook containing worked examples accessible to python users with a range of skill levels. The basic functions of VESIcal can also be accessed via a web app (https://vesical.anvil.app). The VESIcal python library is open-source and available for download at https://github.com/kaylai/VESIcal.