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  1. Abstract

    The transition between blueschist and eclogite plays an important role in subduction zones via dehydration and densification processes in descending oceanic slabs. There are a number of previous petrological studies describing potential mineral reactions taking place at the transition. An experimental determination of such reactions could help constrain the pressure–temperature conditions of the transition as well as the processes of dehydration. However, previous experimental contributions have focused on the stability of spontaneously formed hydrous minerals in basaltic compositions rather than on reactions among already formed blueschist facies minerals. Therefore, this study conducted three groups of experiments to explore the metamorphic reactions among blueschist facies minerals at conditions corresponding to warm subduction, where faster reaction rates are possible on the time scale of laboratory experiments. The first group of experiments was to establish experimental reversals of the reaction glaucophane+paragonite to jadeite+pyrope+quartz+H2O over the range of 2.2–3.5 GPa and 650–820°C. This reaction has long been treated as key to the blueschist–eclogite transition. However, only the growth of glaucophane+paragonite was observed at the intersectional stability field of both paragonite and jadeite+quartz, confirming thermodynamic calculations that the reaction is not stable in the system Na2O–MgO–Al2O3–SiO2–H2O. The second set of experiments involved unreversed experiments using glaucophane+zoisite ±quartz in low‐Fe and Ca‐rich systems and were run at 1.8–2.4 GPa and 600–780°C. These produced omphacite+paragonite/kyanite+H2O accompanied by compositional shifts in the sodium amphibole, glaucophane, towards sodium–calcium amphiboles such as winchite (☐(CaNa)(Mg4Al)Si8O22(OH)2) and barroisite (☐(CaNa)(Mg3Al2)(AlSi7)O22(OH)2). This suggests that a two‐step dehydration occurs, first involving the breakdown of glaucophane+zoisite towards a paragonite‐bearing assemblage, then the breakdown of paragonite to release H2O. It also indicates that sodium–calcium amphibole can coexist with eclogite phases, thereby extending the thermal stability of amphibole to greater subduction zone depths. The third set of experiments was an experimental investigation at 2.0–2.4 GPa and 630–850°C involving a high‐Fe (Fe#=Fetotal/(Fetotal+Mg)≈0.36) natural glaucophane, synthetic paragonite and their eclogite‐forming reaction products. The results indicated that garnet and omphacite grew over most of these pressure–temperature conditions, which demonstrates the importance of Fe‐rich glaucophane in forming the key eclogite assemblage of garnet+omphacite, even under warm subduction zone conditions. Based on the experiments of this study, reaction between glaucophane+zoisite is instrumental in controlling dehydration processes at the blueschist–eclogite transition during warm subduction.

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    Iron-rich phyllosilicates on Mars comprise nearly 90% of the H2O- and OH-bearing phases observed directly by rovers and remotely by orbiters (Chemtob et al., 2017, JGR). Theories concerning the possible origin of Fe-rich smectite during Mars’ earliest history (phyllosian) are hard to test because of limited knowledge of the upper-thermal stability of Fe-rich phyllosilicates. In this study we present data on the upper-thermal stability of a pure-iron smectite to put some minimum constraints on its possible high-temperature origin early in Mars history either from a primordial atmosphere or by hydrothermal activity. Smectite coexisting with quartz and magnetite was synthesized from the oxides in the system Na2O-FeO-Fe2O3-Al2O3-SiO2-H2O at 500°C and 2 kbar and fO2 near FMQ. Reversal experiments involved mixtures with equal portions of the smectite-synthesis and breakdown products (quartz, fayalite, albite, magnetite (mt) treated in the presence of about 10 wt% H2O over the range of 1-3 kbar and 530-640°C. The average composition (electron microprobe) of smectite formed both in synthesis and in reversal experiments was Na0.35(Fe2+2.28Fe3+0.31Al0.41)(Al1.07Si2.93)O10(OH)2·nH2O, where ferric iron was calculated by summing the octahedral cations to 3.0. Reversals for the reaction smec+mt1 = fayalite+albite+mt2+quartz+H2O were obtained at 538±8, 590±10, and 610±10°C at 1, 2, and 3 kbar, respectively, where mt1 and mt2 have the approximate compositions Fe2.8Si0.2O4 and Fe2.8Al0.1O4, respectively, with all other phases being pure. This smectite has up to 2 interlayer H2O at 25°C (and high humidity), losing 1 H2O at <50°C, and the second at 125 ± 25°C. Thermodynamic modeling of this reaction was used to extrapolate the upper-thermal stability of this Fe-smectite down to 10 bars and approximately 239°C. Applications of these results indicate the maximum temperature for forming Fe-smectite from a dense primordial atmosphere of 100 bars is 390 ± 25°C. Crustal storage of water in Fe-smectite ranges up to a maximum of 10.7 wt% at ~2 km and 40°C, 7.4 wt% at 6 km and 120°C, and 3.8 wt% H2O at 32 km and 625°C for a Noachian geotherm of 20°C/km. Plain language summary: This study presents experimental limits on the temperatures at which the clay mineral smectite might form on Mars, either from a dense primordial atmosphere (390°C at 100 bars) or by high-temperature hydrothermal activity (625°C at 32 km). Because this study deals with iron end-member clay, these are minimum temperatures; any solid solution with magnesium will increase these temperatures. 
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  3. ABSTRACT Formation of the feldspathoid sodalite (Na6Al6Si6O24·2NaCl) by reaction of nepheline (NaAlSiO4) with NaCl-bearing brines was investigated at 3 and 6 kbar and at a constant temperature of 750 °C to determine the brine concentration at which sodalite forms with variation in pressure. The reaction boundary was located by reaction-reversal experiments in the system NaAlSiO4–NaCl–H2O at a brine concentration of 0.16 ± 0.08 XNaCl [= molar ratio NaCl/(NaCl + H2O)] at 3 kbar and at a brine concentration of 0.35 ± 0.03 XNaCl at 6 kbar. Characterization of the sodalite using both X-ray diffraction and infrared spectroscopy after treatment in these brines indicated no obvious evidence of water or hydroxyl incorporation into the cage structure of sodalite. The data from this study were combined with earlier results by Wellman (1970) and Sharp et al. (1989) at lower (1–1.5 kbar) and higher (7–8 kbar) pressures, respectively, on sodalite formation from nepheline and NaCl which models as a concave-down curve in XNaCl – P space. In general, sodalite buffers the concentration of neutral aqueous NaCl° in the brine to relatively low values at P < 4 kbar, but NaCl° increases rapidly at higher pressures. Thermochemical modeling of these data was done to determine the activity of the aqueous NaCl° relative to a 1 molal (m) standard state, demonstrating very low activities (<0.2 m, or 1.2 wt.%) of NaCl° at 3 kbar and lower, but rising to relatively high activities (>20 m, or 54 wt.%) of NaCl° at 6 kbar or higher. The results from this study place constraints on the concentration of NaCl° in brines coexisting with nepheline and sodalite and, because of the relative insensitivity of this reaction to temperature, can provide a convenient geobarometer for those localities where the fluid compositions that formed nepheline and sodalite can be determined independently. 
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