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<jats:title>Abstract</jats:title> <jats:p>Control of oxygen fugacity during high-temperature phase equilibrium experiments is required to simulate the conditions that exist in natural systems. At high pressures, oxygen fugacity may be imposed using solid buffer equilibria via the classic “double capsule” technique. This design becomes untenable, however, at temperatures above the melting points of commonly used noble metal capsule materials and/or where buffer assemblages may alloy with the capsule or contaminate the sample. Here we introduce and test a modified double capsule approach that includes a solid metal-oxide buffer in close proximity to but separate from the sample of interest. Buffers used include (in order of most oxidized to reduced) Ni-NiO, Co-CoO, W-WO3, Fe-FeO, Mo-MoO2, Cr-Cr2O3, V-V2O3, Ta-Ta2O5, and Nb-NbO. At a fixed temperature, these buffers span a wide range—up to 10 log fO2 units. To demonstrate the buffering capacity of this double capsule approach, secondary redox equilibria and V-doped CaO-MgO-Al2O3-SiO2 system glasses were studied in experiments using the double capsule geometry. The secondary equilibria provide an independent verification of the oxygen fugacity established in the double capsule environment. The glasses proved difficult to interpret, and our results provide guidance to future efforts to utilize the glass oxybarometer at reducing conditions. Application of this modified double capsule technique to studies of V valence in MgAl2O4 spinels led to the recognition of several factors that will affect V valence in this system: temperature of equilibration, duration of experiment, and spinel bulk composition. We have synthesized V-bearing MgAl2O4 spinel at the reduced conditions of the Cr-Cr2O3, (IW-3.51), Ta-Ta2O5, (IW-5.37), and Nb-NbO buffers (IW-5.44). This spinel exhibits a very small V3+ pre-edge peak consistent with its reduced nature. The absence of evidence for V2+ suggests that MgAl2O4 spinel excludes V2+ due to the preference of V for octahedral sites. This finding is supported by DFT calculations for spinels of variable composition, and in agreement with some other indirect evidence for preference for V3+ in aluminous spinels (Bosi et al. 2016; Paque et al. 2013).</jats:p>

<jats:title>Abstract</jats:title> <jats:p>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 &amp;gt; NNO+2.5.</jats:p> <jats:p>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.</jats:p> <jats:p>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&amp;gt;DCeAnh−Sil, suggest the occurrence of two distinct anhydrite Ca-sites with slightly different optimum radii at the experimental conditions.</jats:p> <jats:p>The ratio DSrAnh−Sil&amp;gt;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.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The presence of water may contribute to compositional heterogeneities observed in the deep lower mantle. Mg-rich ferropericlase (Fp) (Mg,Fe)O in the rock-salt structure is the second most abundant phase in a pyrolitic lower mantle model. To constrain water storage in the deep lower mantle, experiments on the chemical reaction between (Mg,Fe)O and H2O were performed in a laser-heated diamond-anvil cell at 95–121 GPa and 2000–2250 K, and the run products were characterized combining in situ synchrotron X-ray diffraction measurements with ex-situ chemical analysis on the recovered samples. The pyrite-structured phase FeO2Hx (x ≤ 1, Py-phase) containing a negligible amount of Mg (&amp;lt;1 at%) was formed at the expense of iron content in the Fp-phase through the reaction between (Mg,Fe)O and H2O, thus serving as water storage in the deepest lower mantle. The formation and segregation of nearly Mg-free Py-phase to the base of the lower mantle might provide a new insight into the deep oxygen and hydrogen cycles.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Solid iron-silicon alloys play an important role in planetary cores, especially for planets that formed under reducing conditions, such as Mercury. The CsCl (B2) structure occupies a considerable portion of the Fe-Si binary phase diagram at pressure and temperature conditions relevant for the core of Mercury, yet its thermodynamic and thermoelastic properties are poorly known. Here, we report in situ X-ray diffraction measurements on iron-silicon alloys with 7–30 wt% Si performed in laser-heated diamond-anvil cells up to ~120 GPa and ~3000 K. Unit-cell volumes of the B2 phase at high pressures and high temperatures have been used to obtain a composition-dependent thermal equation of state of this phase. In turn, the thermal equation of state is exploited to determine the composition of the B2 phase in hcp+B2 mixtures at 30–100 GPa and to place constraints on the hcp+B2/B2 phase boundary, determined to vary between ~13–18 wt% Si in the considered pressure and temperature range. The hcp+B2/B2 boundary of Fe-Si alloys is observed to be dependent on pressure but weakly dependent on temperature. Our results, coupled with literature data on liquid equations of state, yield an estimation of the density contrast between B2 solid and liquid under Mercury’s core conditions, which directly relates to the buoyancy of the crystallizing material. While the density contrast may be large enough to form a solid inner core by the gravitational sinking of B2 alloys in a Si-rich core, the density of the B2 solid is close to that of the liquid at solidus conditions for Si concentration approaching ~10 wt% Si.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Primary water and oxygen isotope composition are important tools in tracing magma source and evolution. Metamictization of zircon due to U-Th radioactive decay may introduce external secondary water to the crystal, thereby masking the primary water and oxygen isotope signature. Recently, Raman-based screening has been established to select the low-degree metamict zircons. However, such an approach may not be appropriate for ancient samples, in which nearly all zircons are metamict. It was reported that thermal annealing can potentially heal crystals and retrieve primary water content and δ18O information from metamict zircons, given the weaker hydrogen bond of secondary water than that of primary water. Heating experiments at temperatures of 200–1000 °C over a period of 2–10 h reveal that annealing can effectively recover primary water and oxygen isotopes from metamict zircons. Primary water in crystalline and metamict zircons remains intact when heated at &amp;lt;700 °C, while secondary water can be effectively expelled from metamict zircons when heated at 600 °C for &amp;gt;4 h, which represent the optimal annealing treatment condition. Hydrothermally altered zircon is an exception. It only yields the minimum estimate of its primary water contents at 600 °C over a period of &amp;gt;4 h, probably due to partial primary water loss during metamictization for hydrothermal zircons. Moreover, the proportion of low-δ18O (&amp;lt;4.7‰) zircon grains that may be influenced by secondary water dropped from ~21% at &amp;lt;600 °C to ~9% when annealed at &amp;gt;700 °C. This study therefore provides the basis for applying zircon water and δ18O proxies to geologically ancient samples.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The Neoproterozoic peridotites of Abu Dahr, Eastern Desert of Egypt, consist mainly of highly depleted harzburgites that have experienced multiple stages of serpentinization (lizarditization and antigoritization) and carbonation/listvenitization in a forearc environment. The Abu Dahr forearc harzburgites are more oxidized than oceanic mantle, with the oxygen fugacity (fO2) values ranging from FMQ+0.41 to FMQ+1.20 (average = +0.60 FMQ), and were equilibrated at temperatures of 910–1217 °C and pressures of 4.1–7.8 kbar. This study has documented for the first time the presence of various Ni-rich Ni-Fe (-Co) sulfide and metal phases along with Fe-oxides/oxyhydroxides in serpentinized-carbonated peridotites of the Abu Dahr forearc. Here I concentrate on the relationship between redox state and Fe-Ni-Co-O-S minerals with emphasis on the role of hydrothermal processes in upgrading magmatic sulfide tenors, desulfurization (sulfur-loss) of magmatic pentlandite and hydrothermal upgrading of the sulfide phases in Abu Dahr forearc environment. The minerals involved are high-Ni pentlandite (Fe4Ni5S8), cobaltian pentlandite (Fe3.47Ni4.78Co0.75S8), heazlewoodite (Fe0.07Ni2.93S2), godlevskite (Fe0.26Ni8.73Co0.01S8), millerite (Fe0.01Ni0.98Cu0.01S), awaruite (Ni75Fe21) and native Ni (Ni93Fe5), and nickeliferous magnetite and goethite. Chalcopyrite is a rare mineral; other Cu-phases, Fe-sulfides and Ni-arsenides/phosphides are not present. Texturally, Ni-sulfide and alloy minerals occur as interstitial disseminated blebs of either solitary phases or composite intergrowths with characteristic replacement textures, documenting strong variations in oxygen and sulfur fugacities (fO2-fS2). Sulfide assemblages are divided into three main facies: (1) pentlandite-rich; (2) godlevskite-rich; and (3) millerite-rich. Textural relationships imply the following sequence: (a) primary pentlandite → cobaltian pentlandite, with partial replacement of the latter by awaruite and/or heazlewoodite along with magnetite; (b) heazlewoodite is replaced by godlevskite, which in turns is replaced by millerite; (c) Ni-rich awaruite breaks down to millerite; and finally, (d) magnetite is completely replaced by goethite. The sulfide mineralogy reflects the magmatic and post-magmatic evolution of the complex. The primary magmatic processes gave rise to pentlandite, whereas the secondary Ni-sulfides together with the metallic alloys formed in response to changing fO2 and fS2 conditions associated with post-magmatic serpentinization and carbonation. Serpentinization-related Ni-Fe-Co remobilization from magmatic olivines resulted in; (1) upgrading the Ni-Co tenors of pre-existing primary pentlandite, and desulfidation to form low-sulfur sulfides (mainly heazlewoodite) and awaruite under extremely low fO2 and fS2 conditions; (2) in situ precipitation of secondary Ni-sulfides in the presence of extra sulfur as aqueous H2S derived from the desulfurization of magmatic pentlandite or native Ni when fS2 approaches 0; (3) transformation from low-sulfur pentlandite- and godlevskite-rich assemblages to the high-sulfur millerite-rich assemblages related to later carbonation with increasing fO2; and (4) partial dehydration of antigorite serpentinites under high-pressure conditions (&amp;gt;1 GPa) generated Ni-rich awaruite in equilibrium with the prograde assemblage antigorite-metamorphic olivine at higher fO2 and fS2 within subduction channel. The mineralogical, chemical, and thermal similarities with other serpentinite-related Ni-sulfides worldwide suggest that Ni minerals in the Fe-Ni-Co-O-S system record changing fO2 and fS2 during progressive serpentinization and carbonation.</jats:p>

<jats:title>In this issue</jats:title> <jats:p>This issue of New Mineral Names provides a summary of new species that contain arsenic and lead. As of November 2022, there are 1219 minerals that contain constituent arsenic or lead, which is roughly 20% of all known mineral species. These two elements are an important component in many of the newly described minerals that typically form from hydrothermal or other diagenetic processes. Here we look at nitroplumbite, thorasphite, tennantite-(Cd), paradimorphite, tombstoneite, aldomarinoite, lomardoite, dobšináite, panskyite, yugensonite, and kufahrite.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The density of the Earth’s core is several percent lower than that of iron-nickel alloy under conditions of pressure and temperature equivalent to the Earth’s core. Hydrogen is one of the most promising constituents accounting for the density deficit, but hydrogen occupation sites and density decrease of iron-nickel alloy caused by hydrogenation have never been investigated. In this study, the phase relation and crystal structure of Fe0.9Ni0.1Hx(Dx) at high pressures and temperatures up to 12 GPa and 1000 K were clarified by in situ X-ray diffraction and neutron diffraction measurements. Under the P-T conditions of the present study, no deuterium atoms occupied tetragonal (T) sites of face-centered cubic (fcc) Fe0.9Ni0.1Dx, although the T-site occupation was previously reported for fcc FeHx(Dx). The deuterium-induced volume expansion per deuterium vD was determined to be 2.45(4) and 3.31(6) Å3 for fcc and hcp Fe0.9Ni0.1Dx, respectively. These vD values are significantly larger than the corresponding values for FeDx. The vD value for fcc Fe0.9Ni0.1Dx slightly increases with increasing temperature. This study suggests that only 10% of nickel in iron drastically changes the behaviors of hydrogen in metal. Assuming that vD is constant regardless of pressure, the maximum hydrogen content in the Earth’s inner core is estimated to be one to two times the amount of hydrogen in the oceans.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Thermodynamic parameters have been measured for synthetic analogs of the mimetite-group minerals Pb5(AsO4)3X (X = OH, Cl, Br, I) belonging to the apatite supergroup. Phases precipitated from aqueous solutions under ambient conditions with well characterized structures and compositions were studied. For each phase, dissolution enthalpy was experimentally determined by oxide melt drop solution calorimetry in a molten solvent of sodium molybdate (3Na2O·4MoO3) at 976 K. The enthalpy of formation from the elements ΔHf,elo was calculated using thermochemical cycles and was −3030.6 ± 11.5, −3026.6 ± 15.8, −2967.6 ± 25.0, and −2993.1 ± 12.2 kJ/mol for Pb5.00(AsO4)3.00OH0.86(CO3)0.07, Pb5.00(AsO4)3.00Cl0.80(CO3)0.10, Pb5.00(AsO4)3.00Br0.80(CO3)0.10, and Pb5.00(AsO4)3.00I0.45OH0.35(CO3)0.10, respectively. These ΔHf,elo values exhibit typical trends for apatites: they increased (were less negative) with the increasing molar mass and ionic radius of X and decreased with the electronegativity and ionization energy of X. The compilation and comparison of data for Ca-, Pb-, P-, and As-apatites revealed correlations indicating that thermodynamic enthalpic stability is largely influenced by chemical factors (e.g., differences in electronegativities of the elements, ionization energy, or ionic characteristics of the bonds) and to a lesser extent by physical and geometric parameters in the crystal structure related to the mass and size of the X anion. Using the correlations, it was possible to estimate the value of hitherto unknown ΔHf,elo for Pb5(AsO4)3F, −3144.3 ± 66.5 kJ/mol. The observed relationships apply to the entire apatite supergroup and can be used to predict the values of ΔHf,elo for phases that have not been studied experimentally. The new data on environmentally significant phases will contribute to the modeling of mineral-water interactions, particularly for potential use in the remediation of soils and wastes contaminated with Pb and As and in the immobilization of radioactive waste containing I-129.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Heavy meteorite impacts on Earth’s surface produce melt and vapor that are quenched rapidly and scattered over wide areas as natural glasses with various shapes and characteristic chemistry, which are known as tektites and impact glasses. Their detailed formation conditions have long been debated using mineralogical and geochemical data and numerical simulations of impact melt formations. These impact processes are also related to the formation and evolution of planets. To unravel the formation conditions of impact-induced glasses, we performed shock recovery experiments on a tektite. Recovered samples were characterized by X-ray diffraction, Raman spectroscopy, and X-ray absorption fine structure spectroscopy on the Ti K-edge. Results indicate that the densification by shock compression is subjected to post-shock annealing that alters the density and silicate-framework structures but that the local structures around octahedrally coordinated Ti ions remain in the quenched glass. The relationship between the average Ti-O distance and Ti K pre-edge centroid energy is found to distinguish the valance state of Ti ions between Ti4+ and Ti3+ in the glass. This relationship is useful in understanding the formation conditions of impact-derived natural glasses. The presence of Ti3+ in tektites constrains the formation conditions at extremely high temperatures or reduced environments. However, impact glasses collected near the impact sites do not display such conditions, but instead relatively mild and oxidizing formation conditions. These different formation conditions are consistent with the previous numerical results on the crater size dependence.</jats:p>