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The 3.119 ± 0.010 Ma Chefe Donsa phreatomagmatic deposits on the shoulder of the Ethiopian Rift mark the northern termination of the Silti-Debre Zeyit Fault Zone, a linear zone of focused extension within the modern Ethiopian Rift. These peralkaline pumice fragments and glass shards span a wide range of glass compositions but have a restricted phenocryst assemblage dominated by unzoned sanidine. Glass shards found within the ash occupy a far more limited compositional range (75–76 wt% SiO2) in comparison with the pumice (64–75 wt% SiO2), which is rarely mingled. Thermodynamic modeling shows that liquids broadly similar to the least evolved glass composition can be achieved with 50–60 % fractionation of moderately crustally contaminated basalt. Inconsistencies between modeled solutions and the observed values of CaO and P2O5 highlight the important role of fluorine in stabilizing fluor-apatite and the limitations of current thermodynamic models largely resulting from the scarce experimental data available for the role of fluorine in igneous phase stability. On the basis of limited feldspar heterogeneity and crystal content of pumice at Chefe Donsa, and the difficulties of extracting small volumes of Si-rich melt in classical fractional crystallization models, we suggest a two-step polybaric process: (1) basaltic magma ponds at mid-upper-crustal depths and fractionates to form a crystal/magma mush. Once this mush has reached 50–60 % crystallinity, the interstitial liquid may be extracted from the rigid crystal framework. The trachytic magma extracted at this step is equivalent to the most primitive pumice analyzed at Chefe Donsa. (2) The extracted trachytic liquid will rise and continue to crystallize, generating a second mush zone from which rhyolite liquids may be extracted. Some of the compositional range observed in the Chefe Donsa deposits may result from the fresh intrusion of trachyte magma, which may also provide an eruption trigger. This model may have wider application in understanding the origin of the Daly Gap in Ethiopian magmas—intermediate liquids may not be extracted from crystal-liquid mushes due to insufficient crystallization to yield a rigid framework. The wide range of glass compositions characteristic of the proximal Chefe Donsa deposits is not recorded in temporally equivalent tephra deposits located in regional depocenters. Our results show that glass shards, which represent the material most likely transported to distal depocenters, occupy a limited compositional range at high SiO2 values and overlap some distal tephra deposits. These results suggest that distal tephra deposits may not faithfully record the potentially wide range in magma compositions present in a magmatic system just prior to eruption and that robust distal–proximal tephra correlations must include a careful analysis of the full range of materials in the proximal deposit.

The Cindery Tuff is an unusual tephra fall deposit that contains evidence for the mixing of basaltic and rhyolitic liquids prior to eruption. It contains clear rhyolitic glass shards together with brown basaltic glass spheres and a broadly bimodal phenocryst assemblage. Brown glasses are ferrobasaltic in composition and are similar to the voluminous Pliocene tholeiites of the surrounding west-central Afar volcanic field; both are enriched in the light rare earth and incompatible elements and possess higher 87Sr/86Sr and lower 143Nd/144Nd than MORB. Rhyolitic glasses are subalkaline and, compared to the basaltic glasses, are strongly depleted in the compatible elements and enriched in the incompatible elements. Both glass types have similar incompatible element and isotopic ratios, and with the rhyolite glass showing a 2-fold parallel enrichment in rare earth element abundances over the basaltic glass. These observations suggest that the two glasses are genetically related.