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1. Experimental calibration of an Fe3+/Fe2+-in-amphibole oxybarometer and its application to shallow magmatic processes at Shiveluch Volcano, Kamchatka

   https://doi.org/10.2138/am-2022-8031  

   Goltz, Andrea E.; Krawczynski, Michael J.; McCanta, Molly C.; Dyar, M. Darby (November 2022, American Mineralogist)

   Abstract Oxygen fugacity is an important but difficult parameter to constrain for primitive arc magmas. In this study, the partitioning behavior of Fe3+/Fe2+ between amphibole and glass synthesized in piston-cylinder and cold-seal apparatus experiments is developed as an oxybarometer, applicable to magmas ranging from basaltic to dacitic composition. The partitioning of Fe2+ is strongly dependent on melt polymerization; the relative compatibility of Fe2+ in amphibole decreases with increasing polymerization. The Fe2+/Mg distribution coefficient between amphibole and melt is a relatively constant value across all compositions and is, on average, 0.27. The amphibole oxybarometer is applied to amphibole in mafic enclaves, cumulates, and basaltic tephra erupted from Shiveluch volcano in Kamchatka with measured Fe3+/FeTotal. An average Fe3+/Fe2+ amphibole-glass distribution coefficient for basalt is used to convert the Fe3+/FeTotal of amphibole in samples from Shiveluch to magmatic oxygen fugacity relative to NNO. The fO2 of primitive melts at the volcano is approximately NNO+2 and is faithfully recorded in amphibole from an amphibole-rich cumulate and the basaltic tephra. Apparently, higher fO2 recorded by amphibole in mafic enclaves likely results from partial dehydrogenation of amphibole during residence in a shallow andesite storage region. We identify three pulses of mafic magma recharge within two weeks of, a month before, and two to three months before the eruption and find that, at each of these times, the host andesite was recharged by at least two magmas at varying stages of differentiation. Application of the amphibole oxybarometer not only gives insight into magmatic fO2 but also potentially details of shallow magmatic processes. 

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2. Post-melting oxidation of highly primitive basalts from the southern Andes

   https://doi.org/10.1016/j.gca.2020.01.042  

   Tassara, S. (January 2020, Geochimica et cosmochimica acta)

   null (Ed.)

   The oxygen fugacity (fO2) of the Earth’s upper mantle and its melting products is an important parameter in the geochemical evolution of arc magmas and their connection with the continental crustal construction and growth. Several works have focused on the fO2 of peridotite xenoliths, primitive melts in relatively young arc settings, and mid-ocean ridge basalts (MORB) but few studies have attempted to examine the early redox history of primitive magmas in mature arcs. Hence, our understanding of the nature and evolution of fO2 during the subduction cycle remains limited. Here, we investigate the basaltic tephra from the Los Hornitos monogenetic cones in central-southern Chile, which are among the most primitive materials reported in the Southern Andes (olivine Mg#
   92.5, and Ni
   5000 mgg1). These features offer a unique opportunity to explore the fO2 conditions below the Andean arc by studying olivine phenocrysts and their contained crystal and melt inclusions. We integrated EPMA, LA-ICP-MS, and m-XANES analyses to constrain the redox conditions recorded in the basaltic tephra by three different and self-reliant methods. First, we determined the fO2 based on the olivine-spinel equilibrium, yielding average values DFMQ + 1.3 ± 0.4 (1r). Second, we constrained the fO2 conditions of melt inclusions using Fe m-XANES data and the redox dependent olivine-melt vanadium partitioning. After correcting for post-entrapment crystallization and diffusive iron loss, the Fe m-XANES data indicate that the melt inclusions were trapped in average at DFMQ +2.5 ± 0.5 (1r). Results using the olivine-melt vanadium partitioning oxybarometer in melt inclusions are in agreement with Fe m-XANES data, yielding average DFMQ values of +2.6 ± 0.3 (1r). In order to test the potential effects of other postentrapment modifications of the melt inclusions that could have affected the fO2 prior to eruption, we assessed the residence time of these magmas using Mg-Fe interdiffusion modelling in olivine. The short residence times (<200 days) compared to vanadium re-equilibration models strongly suggest that the melt inclusions preserve the prevailing fO2 conditions during their entrapment. Correlations between melt inclusions major element composition and their fO2 determined by Fe m-XANES, as well as V/Sc modelling reveal a case of post-melting oxidation of the LHC magmas. We argue that primitive arc magmas behave as an open system with respect to fO2 during their early geochemical evolution. Our data indicate a complex fO2 early history of primitive melts in the southern Andes and provide a cautionary note on the direct extrapolation of primitive melts fO2 values to that of their mantle source. 

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3. Insights for crystal mush storage utilizing mafic enclaves from the 2011–12 Cordón Caulle eruption

   https://doi.org/10.1038/s41598-022-13305-y  

   Winslow, Heather; Ruprecht, Philipp; Gonnermann, Helge M.; Phelps, Patrick R.; Muñoz-Saez, Carolina; Delgado, Francisco; Pritchard, Matthew; Amigo, Alvaro (December 2022, Scientific Reports)

   Abstract Two distinct types of rare crystal-rich mafic enclaves have been identified in the rhyolite lava flow from the 2011–12 Cordón Caulle eruption (Southern Andean Volcanic Zone, SVZ). The majority of mafic enclaves are coarsely crystalline with interlocking olivine-clinopyroxene-plagioclase textures and irregular shaped vesicles filling the crystal framework. These enclaves are interpreted as pieces of crystal-rich magma mush underlying a crystal-poor rhyolitic magma body that has fed recent silicic eruptions at Cordón Caulle. A second type of porphyritic enclaves, with restricted mineral chemistry and spherical vesicles, represents small-volume injections into the rhyolite magma. Both types of enclaves are basaltic end-members (up to 9.3 wt% MgO and 50–53 wt% SiO 2 ) in comparison to enclaves erupted globally. The Cordón Caulle enclaves also have one of the largest compositional gaps on record between the basaltic enclaves and the rhyolite host at 17 wt% SiO 2 . Interstitial melt in the coarsely-crystalline enclaves is compositionally identical to their rhyolitic host, suggesting that the crystal-poor rhyolite magma was derived directly from the underlying basaltic magma mush through efficient melt extraction. We suggest the 2011–12 rhyolitic eruption was generated from a primitive basaltic crystal-rich mush that short-circuited the typical full range of magmatic differentiation in a single step. 

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4. Origin of the compositionally zoned Paso Puyehue Tephra, Antillanca Volcanic Complex, Chile

   https://doi.org/10.1016/j.jvolgeores.2023.107943  

   DeSilva, Cameron M; Singer, Brad S; Alloway, Brent V; Moreno-Yaeger, Pablo (December 2023, Journal of Volcanology and Geothermal Research)

   The origin of gaps or zoning in the composition of erupted products is critical to understanding how sub-volcanic reservoirs operate. We characterize the compositionally zoned magma that produced the 2053 ± 50 cal. yr BP Paso Puyehue Tephra from the Antillanca Volcanic Complex in the Andean Southern Volcanic Zone (SVZ). The 3.7 km3 Paso Puyehue Tephra is zoned from dacite (69 wt% SiO2) lapilli and ash comprising the lowermost 80% of the deposit that abruptly transitions upward into basaltic andesite scoria (54 wt% SiO2) making up the remaining ~20%. Variations in whole-rock, matrix glass, and mineral compositions through the deposit allow us to estimate pre-eruptive magma storage conditions and to develop a model of how this magma body was generated. Our findings suggest that amphibole-bearing basaltic andesitic magma stored at ~8.0 ± 1.3 km depth fractionally crystallized and cooled from 1048 ± 1.1 to 811 ± 28.6 ◦C under highly oxidizing conditions to produce silicic a melt that upon extraction and rise, pooled at ~6.4 ± 1.2 km depth at temperatures as low as 810 ◦C before eruption. MELTS models suggest that crystallization of a basaltic andesite parent magma with 4 wt% dissolved H2O can produce the dacite under conditions predicted by mineral thermobarometers with phase compositions comparable to those measured in minerals. Pervasive normal zoning at the rims of plagioclase crystals—most pronounced at the transition between dacite and basaltic andesite, and compatible vs. incompatible trace element concentrations, suggest that magma mixing was limited and likely occurred at the interface between the dacitic and basaltic andesitic magmas during ascent within the conduit upon eruption. Compositionally bimodal tephras are increasingly recognized throughout the SVZ with several interpreted to reflect basaltic recharge and mixing into extant rhyolitic reservoirs. In further contrast to other SVZ rhyolitic products, e.g., from the nearby Cord´on Callue and Mocho Choshuenco volcanoes, the Paso Puyehue magma was highly oxidized. This may reflect enhanced delivery of H2O from the subducting plate into the mantle wedge, which in turn may facilitate efficient extraction and separation of buoyant, low-viscosity rhyolitic melt from crystal-rich basaltic andesitic parent magmas and the co-eruption of both end members. 

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5. Crystal Mush Storage Constraints for the Puyehue-Cordon Caulle Volcanic Complex

   Heather Winslow, Philipp Ruprecht (January 2021, AGU Fall Meeting New Orleans, LA & Online Everywhere, 13-17 December 2021)

   Puyehue-Cordon Caulle (PCC) is an active volcanic complex located in the SVZ of the Andes that has had three major historic rhyodacitic eruptions with the most recent event in 2011-12. We provide petrologic and geochemical evidence that PCC is underlain by a crystal mush using recently identified basaltic mafic enclaves that highlights the involvement of distinct mafic magma components during the 2011-12 eruption. We suggest the mafic enclaves represent remnants of the crystal-rich mush that get entrained during eruption of the crystal-poor rhyodacite melt lens cap. This architecture requires the basaltic mush to produce rhyodacite through efficient fractionation. The dominant population of enclaves are equigranular, crystal-rich (45-55%), vesiculated (10-20%), and display interlocking grains between phases. Vesicles have complex shapes filling the irregular interlocking textures, while phenocrysts show stepwise normal zoning (uniform plagioclase cores, ~An90, overgrown with weakly zoned rims, ~An60). A second porphyritic population may represent mafic recharge into the system that bypasses the mush unperturbed. The porphyritic enclaves have spherical vesicles and tightly bound primitive mineral compositions (Fo80-86 vs Fo70-86 in the equigranular enclaves). Published geothermobarometry from the 2011-12 rhyodacite suggests shallow magma storage (5-7 km, 100-140 MPa, 895°C), which we compare against newly determined mineral-mineral trace-element partitioning based thermometry. Our thermometry indicates the equigranular enclaves were stored at ~900-1000°C at the time of eruption suggesting both a compositionally and thermally zoned magma system. We combine this temperature information with trace element data and mass balance calculations from various minerals phases and melt to substantiate our previous hypothesis that the basaltic enclaves can produce rhyodacite given their crystallinity. These estimates may support a spatially connected basaltic crystal-mush underlying a rhyodacite melt lens cap further proving highly efficient rhyolite formation at PCC. PCC’s enclaves present one of the largest compositional gaps on record globally. We compare them to other enclave-bearing systems and how PCC is an important end-member to understand enclaves as well as rhyolite formation. 

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