Pre-1991 sulfur transfer between mafic injections and dacite magma in the Mt. Pinatubo reservoir

Before the 1991–1992 activity, a large andesite lava dome belonging to the penultimate Pinatubo eruptive period (Buag ∼ 500 BP) formed the volcano summit. Buag porphyritic andesite contains abundant amphibole-bearing microgranular enclaves of basaltic–andesite composition. Buag enclaves have lower K₂O and incompatible trace element (LREE, U, Th) contents than mafic pulses injected in the Pinatubo reservoir during the 1991–1992 eruptive cycle. This study shows that Buag andesite formed by mingling of a hot, water-poor and reduced mafic magma with cold, hydrous and oxidized dacite. Depending on their size, enclaves experienced variable re-equilibration during mixing/mingling. Re-equilibration resulted in hydration, oxidation and transfer of mobile elements (LILE, Cu) from the dacite to the mafic melts and prompted massive amphibole crystallization. In Buag enclaves, S-bearing phases (sulfides, apatite) and melt inclusions in amphibole and plagioclase record the evolution of sulfur partition among melt, crystal and fluid phases during magma cooling and oxidation. At high temperature, sulfur is partitioned between andesitic melt and sulfides (Ni-pyrrhotite). Magma cooling, oxidation and hydration resulted in exsolution of a S–Cl–H₂O vapor phase at the S-solubility minimum near the sulfide–sulfate redox boundary. Primary magmatic sulfide (pyrrhotite) and xenocrystic sulfide grains (pyrite), recycled together with olivines and pyroxenes from old mafic intrusives, were replaced by Cu-rich phases (chalcopyrite, cubanite) and, partially, by Ba–Sr sulfate. Sulfides degassed and transformed into residual spongy magnetite in response to fS₂ drop during final magma ascent and decompression. Our research suggests that a complete evaluation of the sulfur budget at Pinatubo must take into account the en route S assimilation from the country rocks. Moreover, this study shows that the efficiency of sulfur transfer between mafic recharges and injected magmas is controlled by the extent and rate of mingling, hydrous flushing and melt oxidation. Vigorous mixing/mingling and transformation of the magmatic recharge into a spray of small enclaves is required in order to efficiently strip their primary S-content that otherwise remains locked in the sulfides. Hydrous flushing increases the magma oxidation state of the recharges and modifies their primary volatile concentrations that cannot be recovered by the study of late-formed mineral phases and melt inclusions. Conversely, S stored in both late-formed Cu-rich sulfides and interstitial rhyolitic melt represents the pre-eruptive sulfur budget immediately available for release from mafic enclaves during their decompression.