The ~5 km3, 4.54–4.09 Ma Caspana ignimbrite of the Altiplano-Puna volcanic complex (APVC) of the Central Andes records the eruption of an andesite and two distinct rhyolitic magmas. It provides a unique opportunity to investigate the production of silicic magmas in a continental arc flare-up, where small volumes of magma rarely survive homogenization into the regional magmatic system that is dominated by supereruptions of monotonous dacitic ignimbrites. The fall deposit and thin flow unit that record the first stage of the eruption (Phase 1) tapped a crystal-poor peraluminous rhyolite. The petrological and geochemical characteristics of Phase 1 are best explained by partial melting of or reheating and melt extraction from a granodioritic intrusion. Phase 2 of the eruption records the emplacement of a more extensive flow unit with a crystal-poor, fayalite-bearing rhyolite and a porphyritic to glomeroporphyritic andesite containing abundant plagioclase-orthopyroxene-Fe-Ti oxide (norite) glomerocrysts. The isotopic composition of Phase 2 is significantly more “crustal” than Phase 1, indicating a separate petrogenetic path. The mineral assemblage of the noritic glomerocrysts and the observed trend between andesite and Phase 2 rhyolite are reproduced by rhyolite-MELTS–based models. Pressure-temperature-water (P-T-H2O) estimates indicate that the main (Phase 2) reservoir resided between 400 and 200 MPa, with the andesite recording the deeper pressures and a temperature range of 920–1060 °C. Rhyolite phase equilibria predict an estimated temperature of ~775 °C and ~5 wt% H2O. Pressures derived from phase equilibria indicate that the rhyolite was extracted directly from the noritic cumulate at ~340 MPa and stored at slightly shallower pressures (200–300 MPa) prior to eruption. The rhyolite-MELTS models reveal that latent-heat buffering during the extraction and storage process results in a shallow liquidus during the extensive crystallization that produced a noritic cumulate in equilibrium with a rhyodacitic residual liquid. Spikes in latent heat facilitated the segregation of the residual liquid, creating the pre-eruptive compositional gap of ~16 wt% SiO2 between the andesite and the Phase 2 rhyolite. Unlike typical Altiplano-Puna volcanic complex (APVC) magmas, low ƒO2 conditions in the andesite promoted co-crystallization of orthopyroxene and ilmenite in lieu of clinopyroxene and magnetite. This resulted in relatively high Fe concentrations in the rhyodacite and Phase 2 rhyolite. Combined with the co-crystallization of plagioclase, this low oxidation state forced high Fe2+/Mg and Fe/Ca in the Phase 2 rhyolite, which promoted fayalite stability. The dominance of low Fe3+/FeTot and Fe-Ti oxide equilibria indicates low ƒO2 (ΔFMQ 0 − ΔFMQ − 1) conditions in the rhyolite were inherited from the andesite. We propose that the serendipitous location on the periphery of the regional thermal anomaly of the Altiplano-Puna magma body (APMB) permitted the small-volume magma reservoir that fed the Caspana ignimbrite eruption to retain its heterogeneous character. This resulted in the record of rhyolitic liquids with disparate origins that evaded assimilation into the large dacite supereruption-feeding APMB. As such, the Caspana ignimbrite provides a unique window into the multiscale processes that build long-lived continental silicic magma systems.
Anhydrite has become increasingly recognized as a primary igneous phase since its discovery in pumices from the 1982 eruption of El Chichón, Mexico. Recent work has provided evidence that immiscible sulfate melts may also be present in high-temperature, sulfur-rich, arc magmas. In this study we present partition coefficients for 37 trace elements between anhydrite, sulfate melt and silicate melt based on experiments at 0.2–1 GPa, 800–1200 °C, and fO2 > NNO+2.5. Sulfate melt–silicate melt partition coefficients are shown to vary consistently with ionic potential (the ratio of nominal charge to ionic radius, Z/r) and show peaks in compatibility close to the ionic potential of Ca and S. Partition coefficients for many elements, particularly REE, are more than an order of magnitude lower than previously published data, likely related to differences in silicate melt composition between the studies. Several highly charged cations, including V, W, and Mo are somewhat compatible in sulfate melt but are strongly incompatible in anhydrite. Their concentrations in quench material from natural samples may help to fingerprint the original presence of sulfate melt. Partition coefficients for 2+ and 3+ cations between anhydrite and silicate melt vary primarily as a function of the calcium partition coefficients (DCaAnh−Sil) and can be described in terms of exchange reactions involving the Ca2+ site in anhydrite. Trivalent cations are dominantly charge-balanced by Na1+. Most data are well fit using a simple lattice-strain model, although some features of the partitioning data, including DLaAnh−Sil>DCeAnh−Sil, suggest the occurrence of two distinct anhydrite Ca-sites with slightly different optimum radii at the experimental conditions. The ratio DSrAnh−Sil>DCaAnh−Sil is shown to be relatively insensitive to silicate melt composition and should vary from 0.63–0.53 between 1200–800 °C, based on a simple, “one-site” lattice strain model. Comparison to DSrAnh−Sil and DCaAnh−Sil calculated for natural anhydrite suggests that in most cases, including the S-rich eruptions of Pinatubo and El Chichón, the composition of anhydrite is consistent with early crystallization of anhydrite close to the liquidus of silicate melt with a composition approximately that of the bulk erupted material. This illustrates how anhydrite (and perhaps sulfate melt) provides a mechanism to transport large quantities of sulfur from significant depth to the eruptive environment.
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