Variable Partitioning of Lithium in Rhyolitic Melt During Decompression and Ascent

The partitioning behavior of Li in magmatic systems is increasingly being investigated due to the economic importance of Li in the transition to sustainable energy resources (e.g., batteries). However, at upper crustal pressures, it remains uncertain whether Li preferentially partitions into the vapor or liquid (brine) phase or remains in the silicate melt. This complicates our ability to determine where Li resides—silicate melt, minerals, or fluid phase—upon eruption, a crucial factor for understanding its postdepositional movement and concentration into a brine or volcano-sedimentary deposit. Here, we present a novel investigation into the behavior of Li within natural evolved melts during continuous magma decompression and ascent using melt embayments (open melt inclusions). Mineral-hosted melt embayments preserve records of the evolving composition of the exterior melt, including degassing pathways and ascent timescales, when paired with appropriate diffusion coefficients. Lithium concentration profiles were measured in quartz-hosted melt embayments from the rapidly quenched eruptive phases of five rhyolitic, caldera-forming eruptions to investigate the behavior of Li during magma decompression and ascent, where vapor partitioning and ascent dynamics were previously established by investigating H2O and CO2 profiles. We find that in four systems, embayments contain lower interior Li concentrations than the coerupted melt inclusions; the fifth system contains the same Li concentrations in embayments and melt inclusions. However, many of these embayments contain gradients, with 84% preserving Li enrichment near the melt-bubble interface, as compared to their interior concentration. We interpret these characteristics to represent two distinct stages of Li partitioning during magma decompression and ascent, in contrast to existing literature that proposes only one type of partitioning behavior. The first stage is interpreted as melt depletion of Li, likely driven by partitioning into an exsolved supercritical fluid phase, supported by the strong correlation between the extent of Li depletion and Cl concentration in the melt, as well as the decompression rate. This behavior then fundamentally shifts, where Li reenriches in the melt, postulated to be driven by the unmixing of the supercritical fluid phase at shallow pressures. For the one system that did not develop Li gradients through decompression, we attribute this to the lower values of Na and Cl in the melt, potentially inhibiting the partitioning of Li into a fluid phase. Importantly, the behavior of Li during decompression is not consistent within or between volcanic centers, highlighting the need for systematic experimental investigation in variable composition melts at pressures relevant to conduit dynamics. This knowledge would improve our ability to model Li profiles to understand magma decompression, and predict where Li resides (e.g., stored in volcanic glass, gas, or crystals) upon eruption prior to any later extraction.