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<jats:title>Abstract</jats:title> <jats:p>We report a first-principles-based thermodynamic investigation of the interplay between cation inversion and twinning in MgAl2O4 spinel (MAS). We examine the atomic-scale structure of (111) twins and characterize the local octahedral and tetrahedral distortions. We observe that the asymmetric nature of polyhedral distortions about the (111) twin plane causes anisotropy in cation inversion energies near the planar fault. The predicted enthalpies and entropies of inversion reveal that in comparison to the Kagome layer, the anti-site occupancies of Al and Mg, i.e., cation inversion, on the mixed-cation-layer near the twin boundary are more favorable and stable in the entire range of temperature of twin stability. Structurally, such a stable inversion is necessitated by the minimization in the polyhedral distortions, especially by the octahedral distortion, which exhibits a reduction of four orders of magnitude relative to the polyhedra with no inversion. The fundamental understanding obtained on the thermodynamics of the twin-cation inversion interplay in conjunction with the kinetics of inversion was used as a basis for developing a thermochronometer for deducing the temperature of twinning in MAS. This work serves as an important steppingstone for experimental characterization of MAS structures within a host of Earth and planetary materials. In the case of the latter, our results enable the use of planar faults, such as twins, as important markers for deducing the physical and chemical landscape that MAS experienced in its evolution and transport within the solar protoplanetary disk.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Growth of reaction rims is mainly controlled by a change in physical parameters such as pressure and temperature, a change in the chemical composition of the system, and/or by the presence of volatiles. In particular, the effect of volatiles other than water on reaction-rim growth remains poorly understood. To accurately model metamorphic and metasomatic processes, a quantification of the effect of volatiles on reaction-rim growth dynamics is necessary but hitherto missing.</jats:p> <jats:p>In this study, reaction rims were experimentally grown in a series of piston-cylinder experiments in the ternary CaO-MgO-SiO2 system at 1000 °C and 1.5 GPa with 0–10 wt% F for 20 min. In the fluorine-free system, a rim sequence of wollastonite (Wo) | merwinite (Mer) | diopside (Di) | forsterite (Fo) | periclase (Per) formed, complying with the stable phase configuration at water-saturated conditions. As soon as 0.1 wt% F was introduced into the system, humite group minerals (HGMs) and monticellite (Mtc) appeared, resulting in the multilayer rim sequence Wo | Mer | Mtc | Fo + HGMs | Per. In experiments with fluorine concentrations ≥0.5 wt%, cuspidine (Csp) appears in the layer sequence and represents the major fluorine sink. Our data show that the addition of fluorine may stabilize the fluorine-bearing phases cuspidine and HGMs to higher temperatures, which is in agreement with previous studies (Grützner et al. 2017). However, the appearance of the nominally anhydrous minerals (NAMs) monticellite and åkermanite (Ak) at this P-T condition suggests that the addition of fluorine may also affect the stability of nominally fluorine-free minerals. This may be explained by the effect of fluorine on the Gibbs free energies of fluorine-bearing phases, which in turn affects the relative Gibbs free energies and thus the stabilities of all phases. An increase in absolute rim thickness from 11.8(21) to 105.6(22) µm (1σ standard deviations in parentheses) in fluorine free and 10 wt% F experiments, respectively, suggests that fluorine enhances absolute component mobilities and thus results in faster rim growth rates. Additionally, due to the presence of fluorine, a change in relative component mobilities results in microstructural changes such as a phase segregation of diopside and cuspidine at high-fluorine (≥3 wt% F) concentrations.</jats:p> <jats:p>These results not only imply that reaction rims may be used as a tool to infer the amount of fluorine present during metamorphic reactions but also that we need to consider the role of fluorine for a correct interpretation of the P-T-t history of metamorphic and metasomatic rocks.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The Lewisian Complex in northwest Scotland presents a record of the transition from the Neo-Archean to the Paleoproterozoic. However, this record is complicated by a long and varied history after peak metamorphism that has erased and/or partially reset much of the early history of the rocks. Such overprinting is a common feature of Archean granulites and poses a substantial problem when trying to understand the tectonic processes that were active prior to the onset of modern plate tectonics.</jats:p> <jats:p>By combining careful petrography with phase diagram modeling and a range of exchange thermometers we obtain the peak and retrograde temperature history of the Lewisian Complex from a single, well-preserved, representative sample of garnet-bearing mafic granulite. We present the application of high-resolution electron probe microanalysis (HR-EPMA) to characterize sub-micrometer orthopyroxene exsolution lamellae in clinopyroxene. We discuss ways to mitigate issues associated with HR-EPMA including surface contamination, beam drift, standards, and the need to correct for secondary fluorescence effects. The resulting compositions from our HR-EPMA analyses provide an independent measure of the retrograde temperature conditions and can also be used to back-calculate the compositions of clinopyroxene in the peak assemblage.</jats:p> <jats:p>We obtain peak metamorphic conditions for the Lewisian of &amp;gt;11 kbar and &amp;gt;1025 °C, and constrain subsequent metamorphic overprints to 850 °C (Grt-Cpx), 590 °C (Opx-Cpx), and 460 °C (Mag-Ilm). These peak and retrograde temperatures span the range of those found in the literature. Whereas recent phase equilibrium studies assume equilibrium among all preserved high-T minerals, this study considers microstructural and mineral-chemical evidence for corona formation that reflects post-peak decompression with partial equilibration at ~850 °C, as recognized in some earlier studies.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Interphase boundaries are planar defects that separate two different minerals, which in general have different compositions and/or crystalline structures; they may play an important role as a pathway for fluids in rocks and affect their physical properties. To completely characterize interphase boundaries, one needs to define the misorientation between adjacent grains and the orientation of the grain boundary plane. The analysis performed here is limited to the misorientation characterization and the trace of the interphase boundary. Although the determination of possible orientation relationships between the two adjacent phases is routinely performed by selected-area electron diffraction in a transmission electron microscope, this method lacks statistical representativeness. With the advent of techniques like electron backscatter diffraction (EBSD), it is possible to calculate orientation relationships not only in single pairs of crystals of the same phase but in full thin sections and between different minerals. The interphase misorientation is calculated from two orientations of two adjacent crystals of different phases. A set of single misorientations is then used to calculate the misorientation distribution function (MDF), from where it is possible to identify a maximum and its crystallographic interpretation. If we then know the misorientation and the unit-cell parameters of the individual phases, the crystal-lographic relationships between the different phases can be described with the pairs of parallel crystal-lographic planes and the pairs of crystallographic directions. In this paper, I present examples of the use of interphase misorientation analysis on the transformation of calcite-aragonite, olivine-antigorite, magnetite-hematite, and on the study of orientation relationships between plagioclase-olivine-ilmenite in mid-ocean ridges gabbros (ODP Hole 735).</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Mineral/melt partition coefficients have been widely used to provide insights into magmatic processes. Olivine is one of the most abundant and important minerals in the lunar mantle and mare basalts. Yet, no systematic olivine/melt partitioning data are available for lunar conditions. We report trace element partition data between host mineral olivine and its melt inclusions in lunar basalts. Equilibrium is evaluated using the Fe-Mg exchange coefficient, leading to the choice of melt inclusion-host olivine pairs in lunar basalts 12040, 12009, 15016, 15647, and 74235. Partition coefficients of 21 elements (Li, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Co, Y, Zr, Nb, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) were measured. Except for Li, V, and Cr, these elements show no significant difference in olivine-melt partitioning compared to the data for terrestrial samples. The partition coefficient of Li between olivine and melt in some lunar basalts with low Mg# (Mg# &amp;lt; 0.75 in olivine, or &amp;lt; ~0.5 in melt) is higher than published data for terrestrial samples, which is attributed to the dependence of DLi on Mg# and the lack of literature DLi data with low Mg#. The partition coefficient of V in lunar basalts is measured to be 0.17 to 0.74, significantly higher than that in terrestrial basalts (0.003 to 0.21), which can be explained by the lower oxygen fugacity in lunar basalts. The significantly higher DV can explain why V is less enriched in evolved lunar basalts than terrestrial basalts. The partition coefficient of Cr between olivine and basalt melt in the Moon is 0.11 to 0.62, which is lower than those in terrestrial settings by a factor of ~2. This is surprising because previous authors showed that Cr partition coefficient is independent of fO2. A quasi-thermodynamically based model is developed to correlate Cr partition coefficient to olivine and melt composition and fO2. The lower Cr partition coefficient between olivine and basalt in the Moon can lead to more Cr enrichment in the lunar magma ocean, as well as more Cr enrichment in mantle-derived basalts in the Moon. Hence, even though Cr is typically a compatible element in terrestrial basalts, it is moderately incompatible in primitive lunar basalts, with a similar degree of incompatibility as V based on partition coefficients in this work, as also evidenced by the relatively constant V/Cr ratio of 0.039 ± 0.011 in lunar basalts. The confirmation of constant V/Cr ratio is important for constraining concentrations of Cr (slightly volatile and siderophile) and V (slightly siderophile) in the bulk silicate Moon.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The use of the field emission gun in scanning electron microscopy permits the imaging of submicrometer-size features. However, achieving sub-micrometer analytical spatial resolution in electron probe microanalysis (EPMA) requires both reducing the electron beam size and reducing the accelerating voltage to achieve the desired sub-micrometer interaction volume. The resulting quantification of the first-row transition metals at low accelerating voltage, i.e., below 7–8 kV, is problematic as the main characteristic X-ray lines (Kα) cannot be excited at these conditions. Furthermore, the use of the Lα and Lβ soft X-ray lines for quantification is complicated by bonding and self-absorption effects resulting in not-yet-determined mass absorption coefficients and hence in the failure of the traditional matrix correction procedure. We propose two methods to circumvent these low-kilovolt (low-kV) analysis limitations: using the non-traditional FeLℓ line and using universal calibration curves for the more traditional FeLα and Lβ lines. These methods were successfully applied to Fe-sulfide minerals showing accurate quantification results by EPMA at reduced kV, necessary for accurate quantification of sub-micrometer sulfide grains.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The relationship between plutonic and volcanic components of magmatic plumbing systems continues to be a question of intense debate. The Oki-Dōzen Islands, Sea of Japan, preserve outcrops of temporally associated plutonic, hypabyssal, and volcanic rocks. Post-intrusion uplift juxtaposed Miocene syenites in inferred faulted contact with volcanic trachytes that are cut by rhyolite hypabyssal dikes. This provides a window deep into the timing and origins of magma storage architecture and dynamics. Zircon is ubiquitous in all samples; our aim is to determine what its age and composition can reveal about the plutonic-volcanic connection. Here we show magma source characteristics are recorded in zircon Hf isotopes; source composition and assimilation of heterogeneous hydrothermally altered crust in zircon O isotopes; and extensive fractional crystallization in zircon trace elements. Combined with new UTh-Pb SHRIMP zircon ages, 6.4–5.7 Ma, compositional data show pluton formation was by protracted amalgamation of discrete magma pulses. The rhyolite dike preserves an evolved fraction segregated from these discrete magmas. Synchronous with plutonism was a volcanic eruption of trachyte magma derived from the same source, which may have stalled at a relatively shallow depth prior to eruption. Stalling occurred at least above the amphibole stability zone because amphibole-compatible Sc and Ti were not depleted in the trachyte melt resulting in elevated values of these in volcanic compared to plutonic zircon. Identifying smaller episodic magma pulses in a larger magmatic complex places constraints on potential magma fluxes and eruptible volumes. High-flux, large volume, plume-related ocean island magmatic systems may have extensive vertically distributed multi-stage magmatic reservoirs and subduction-related systems transcrustal magma reservoirs. By contrast, Oki-Dōzen was a low-flux system with incremental pluton growth and small- to moderate-scale eruptions.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>For the first time, cathodoluminescence (CL) was used to show oscillatory zoning in perthitic K-feldspars from the equigranular Toki granite, central Japan. Based on the CL patterns, two types of zoning are identified: single core oscillatory zoning (SCOZ) and multiple core oscillatory zoning (MCOZ). The SCOZ is defined by oscillatory zoning around a single-crystal core within the K-feldspar crystal, whereas the MCOZ depicts two or more such crystal cores. The crystal cores displayed in CL images reflect the nucleation parts of magmatic K-feldspar. The existence of MCOZ patterns in K-feldspars indicates multiple nuclei. CL patterns reveal crystal growth behavior of magmatic K-feldspar in the equigranular Toki granite. CL intensities are positively correlated with titanium and barium concentrations, indicating that the CL variations depend on two factors: (1) titanium concentration as a CL activator and (2) density of Al-O−-Al structural defects. The analysis of CL images revealed that albite-rich phases in microperthite and patchperthite with low-luminescence intensities cut across the CL bands of the oscillatory zoning, indicating that the oscillatory zoning in the orthoclase-rich host phase of K-feldspar was not perturbed by the formation of microperthite and patchperthite in the post-crystallization stage. The luminescence intensities of albite-rich phases in patchperthite are lower than those in microperthite, which is due to the differences in titanium and barium concentrations between them. In the post-crystallization stage, the mass transfer of titanium and barium occurred during the formation of microperthite and patchperthite. Therefore, the difference in the luminescence intensities between microperthite and patchperthite lamellae reflects their different formation mechanisms between exsolution coarsening and dissolution-precipitation coarsening. In summary, CL analyses can be used for the evaluation of the nucleation and growth not only of anhedral K-feldspar crystals in equigranular granite but also of K-feldspar phenocrysts/megacrysts in porphyritic granite. It can reveal the spatial extent of element partitioning between the melt and crystal, along with that of mass transfer from the melt into crystals during the magma evolution. Moreover, the CL analyses can also be used for the interpretation of K-feldspar textural development during the post-crystallization stage.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Piston-cylinder assemblies exhibit inhomogeneous pressure distributions and biases compared to the theoretical pressure applied to the hydraulic press because of the thermal and mechanical properties of the assembly components. Whereas these effects can partially be corrected by conventional calibration, systematic quantification of friction values remain very sparse and results vary greatly among previous studies. We performed an experimental study to investigate the behavior of the most common cell assemblies, i.e., talc [Mg3Si4O10(OH)2], NaCl, and BaCO3, during piston-cylinder experiments to estimate the effects of pressure, temperature, run duration, assembly size, and assembly materials on friction values. Our study demonstrates that friction decreases with time and also partially depends on temperature but does not depend on pressure. We determined that friction decreases from 24 to 17% as temperature increases from 900 to 1300 °C when using talc cells, indicating a friction decrease of ~2% per 100 °C increase for 24 h experiments. In contrast, friction becomes independent of time above 1300 °C. Moreover, at a fixed temperature of 900 °C, friction decreases from 29% in 6 h runs to 21% in 48 h runs, corresponding to a decrease of friction of 0.2% per hour. Similar results obtained with NaCl cell assemblies suggest that friction is constant within error, from 8% in 9 h runs to 5% in 24 h runs. At 900 °C, possible steady-state friction values are only reached after at least 48 h, indicating that friction should be considered a variable for shorter experiments. We establish that assembly materials (and their associated thermomechanical properties) influence the friction correction more than the dimensions of the assembly parts. Finally, we show that the use of polytetrafluoroethylene film instead of conventional Pb foil does not modify friction but significantly reduces the force required for sample extraction, thus increasing the lifetime of the carbide core, which in turn enhances experimental reproducibility.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Aluminum-rich and Si-poor calcium amphibole [~3.9 Al atoms per formula unit (apfu) and ~5.5 Si apfu for 23 O] occur in the quartz-bearing eclogites from the Donghai area, Sulu ultrahigh-pressure metamorphic belt, eastern China. Most of the aluminous amphibole phases are retrograde products from the exhumation and hydration stage and are texturally divided into a mantle phase around a porphyroblastic garnet and a crack-filling (vein) phase of a garnet. Less aluminous amphibole occurs as symplectite phase with plagioclase after omphacite. The formation process of the aluminous amphibole in the quartz-bearing samples is discussed on the basis of the analytical data by EPMA, FIB-TEM, and EBSD.</jats:p> <jats:p>The mantle amphibole occurs between garnet and symplectite or quartz. A set of plagioclase and aegirinediopside/argirine-hedenbergite thin monomineralic bands forms at the boundary between the mantle amphibole and matrix quartz. However, these monomineralic bands do not occur at the mantle amphibole-symplectite boundary. These textural differences indicate that the recrystallization of the aluminous amphibole around garnet was controlled by significant local reactions, and the size of equilibrate domains was probably several tens of micrometers or less.</jats:p> <jats:p>The mantle amphibole is composed of inner (garnet-side) and outer (matrix-side) zones. The inner zone is compositionally homogeneous, and its atomic Al/Si value is ~0.63–0.66 and similar to that of garnet. Atomic Ca/Si value in the inner zone is also almost uniform and is generally identical to that of garnet. The outer zone exhibits a monotonic decrease in the Al/Si and Ca/Si values outward, and its composition at the outermost margin is similar to that of the symplectitic amphibole. The crack-filling amphibole has a composition similar to the inner zone of the mantle amphibole. The CPO pattern of the crack-filling amphibole is different from that of the adjacent mantle amphibole, showing that the crack-filling amphibole is cut by the mantle amphibole. The textural relationship between the mantle and crack-filling amphibole phases and their compositional characteristics imply that: (1) the mantle type is a slightly later stage product than the crack-filling type, and (2) the boundary between the inner and outer zones of the mantle aluminous amphibole probably corresponds to the initial surface of the porphyroblastic garnet. The inner zone is considered to have grown inward by simple substitution of garnet, using the tetrahedral and octahedral cations of the garnet as the basic framework. On the other hand, most of the outer zone of the mantle-type amphibole grew outward in the matrix from the initial surface of the garnet porphyroblast. The mantle amphibole shows a CPO similar to that of amphibole in the adjacent symplectite domain, suggesting that these two types of amphibole formed almost simultaneously, sharing crystallographic orientation with each other.</jats:p> <jats:p>The formation of crack-filling aluminous amphibole was probably promoted by the hydraulic microfrac-turing process at an early stage of exhumation and hydration. The mantle and symplectitic amphibole phases formation was promoted by the subsequent infiltration of metamorphic fluid. The aluminous amphibole in the SiO2 phase-bearing eclogites probably recrystallized with the formation of a localized SiO2-undersaturated reaction domain because of rapid exhumation and subsequent rapid cooling of the Sulu UHP metamorphic belt.</jats:p>