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<jats:title>Abstract</jats:title> <jats:p>Halogens and other volatiles are widely recycled into the deep mantle by subduction and are key components to metasomatize the sub-continental lithospheric mantle (SCLM). Lamprophyres are well known to be rich in volatiles and are important for understanding the halogen characteristics of the meta-somatized SCLM and/or the mobilization of halogens during the ascent of such volatile-rich, low-degree partial melts. The North China Craton (NCC) hosts lamprophyre dikes coeval with extensive thinning of the eastern NCC in the Mesozoic and generated from lithosphere metasomatized by multiple-stage subduction components. Here we report bulk-rock heavy halogens (Cl, Br, and I) of 16 lamprophyres from the eastern NCC. The bulk-rock halogen concentrations are overall very low (Cl = 58–170 μg/g, Br = 285–559 ng/g, and I &amp;lt;5 ng/g), comparable with depleted Mid-Ocean ridge basalts (N-MORBs). Volatile-rich minerals (e.g., amphibole and biotite) are abundant (20–30 vol%) in these lamprophyres, however, electron probe microanalyses (EPMA) data indicate that amphiboles are mainly rich in OH and F but display very low Cl concentrations (0.01–0.04 wt%). The bulk rock and amphibole data consistently indicate low abundances of heavy halogens in the lamprophyres, which is difficult to reconcile with the remarkable enrichment of fluid-mobile large ion lithophile elements such as Ba, Rb, and K. Based on low Cl/Nb and Br/Nb but high Ba/Nb and K/Nb ratios, the low halogen concentrations likely resulted from extensive volatile loss (&amp;gt;90%) during melt ascent. The low Cl concentrations in early-stage amphiboles (Mg# 60–64) further indicate that such loss would have occurred before amphibole crystallization at a depth of ~15 km. We thus propose that crystallization of early olivines and pyroxenes and reaction with surrounding mantle rocks likely induced volatile saturation and exsolution, leading to strong partitioning of the halogens into the exsolved aqueous volatile phases and thus the extensive loss of halogens from the rising melt. These results reveal that significant volatile loss of halogens not only occurs during surficial low-pressure eruption but also at much deeper levels in the crust, as also identified for some kimberlites. Consequently, it would be difficult to constrain the primitive halogen components of the mantle sources via lamprophyres or similar magmas.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Ba-, Ti-, and Cl-rich micas associated with other Ba- and/or Cl-rich minerals in the rock matrix or in garnet and clinopyroxene hosted multiphase solid inclusions (MSI) are observed in mantle-derived garnet pyroxenites. The micas show extremely high variability in chemical composition ranging between Ba-rich phlogopite, chloroferrokinoshitalite, and oxykinoshitalite. Elemental covariation trends in mineral chemical data reveal the principal substitution mechanisms responsible for the observed chemical variability. The substitution Ba2+Al3+ ↔ K1+Si4+ associated with either OH1– ↔ Cl1– or Ti4+2O2– ↔ Mg2+2OH1 links phlogopite to chloroferrokinoshitalite and oxykinoshitalite, respectively, whereas the substitution Ti4+2O2– ↔ Fe2+2Cl1– links chloroferrokinoshitalite to oxykinoshitalite. The preferred incorporation of Cl in Fe-rich mica and of Ti+O in Mg-rich mica indicates that XFe (Fetot/Fetot+Mg) exerts an important control on mica composition. The positive correlation of XFe with Cl led to the formation of possibly the most Cl-rich mica so far described classified as chloroferrokinoshitalite (XFe0.88, Ba0.95K0.03Fe2.68Mg0.37Al1.91Si2.01Cl1.98) with 10.98 wt% Cl. Substantial substitution of OH– by Cl– and O2– in mica, and the presence of Cl-apatite, a rare Cl-rich phosphate goryainovite, and carbonates together with Cl-rich micas indicate high-Cl and -CO2 activity and low-H2O activity in metasomatizing fluids or melts that may be classified as Ba-Cl-rich silicocarbonatitic. The coexistence of two micas with distinct compositions close to chloroferrokinoshitalite (XFe0.57–0.77, K~0.1Ba0.6–0.8Mg0.7–1.3Fe1.7–2.3Ti0.0–0.1 Si2.2–2.3Al1.5–1.7Cl1.2–1.8) and oxykinoshitalite (XFe0.19–0.20, K~0.3Ba~0.5Mg2.0–2.1Fe~0.5Ti0.2–0.4Si2.4–2.6Al~1.8Cl~0.3) suggests that a miscibility gap exists between these two compositions. The exotic mineral assemblage was formed by interaction with metasomatizing fluids or melts whose origin cannot be defined with certainty. They may be derived from crustal or mantle lithologies or from the host garnet pyroxenites. The textural position of the MSI in garnet and their characteristic mineral assemblages indicate that they have been introduced into the garnet crystals under post-peak conditions, possibly during decompression. With this research we document substitution mechanisms in Ba-, Ti-, and Cl-rich micas and shed light on the behavior and composition of fluids or melts at the upper mantle/lower crust interface.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Fluid-mediated calcium metasomatism is often associated with strong silica mobility and the presence of chlorides in solution. To help quantify mass transfer at lower crustal and upper mantle conditions, we measured quartz solubility in H2O-CaCl2 solutions at 0.6–1.4 GPa, 600–900 °C, and salt concentrations to 50 mol%. Solubility was determined by weight loss of single-crystals using hydrothermal piston-cylinder methods. All experiments were conducted at salinity lower than salt saturation. Quartz solubility declines exponentially with added CaCl2 at all conditions investigated, with no evidence for complexing between silica and Ca. The decline in solubility is similar to that in H2O-CO2 but substantially greater than that in H2O-NaCl at the same pressure and temperature. At each temperature, quartz solubility at low salinity (XCaCl2 &amp;lt; 0.1) depends strongly on pressure, whereas at higher XCaCl2 it is nearly pressure independent. This behavior is consistent with a transition from an aqueous solvent to a molten salt near XCaCl2 ~0.1. The solubility data were used to develop a thermodynamic model of H2O-CaCl2 fluids. Assuming ideal molten-salt behavior and utilizing previous models for polymerization of hydrous silica, we derived values for the activity of H2O (aH2O), and for the CaCl2 dissociation factor (α), which may vary from 0 (fully associated) to 2 (fully dissociated). The model accurately reproduces our data along with those of previous work and implies that, at conditions of this study, CaCl2 is largely associated (&amp;lt;0.2) at H2O density &amp;lt;0.85 g/cm3. Dissociation rises isothermally with increasing density, reaching ~1.4 at 600 °C, 1.4 GPa. The variation in silica molality with aH2O in H2O-CaCl2 is nearly identical to that in H2O-CO2 solutions at 800 °C and 1.0 GPa, consistent with the absence of Ca-silicate complexing. The results suggest that the ionization state of the salt solution is an important determinant of aH2O, and that H2O-CaCl2 fluids exhibit nearly ideal molecular mixing over a wider range of conditions than implied by previous modeling. The new data help interpret natural examples of large-scale Ca-metasomatism in a wide range of lower crustal and upper mantle settings.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Boron nitride (BN) is a commonly used pressure-transmitting material in experimental petrology. It is often considered to be as inert as MgO or Al2O3, and its redox potential is seldomly discussed. It is generally implied that, when used as a capsule sleeve, BN may impose relatively reduced conditions, similar to the effect of the fayalite-magnetite-quartz (FMQ) buffer. However, sediment melting experiments performed at 1050 °C and 3 GPa with BN as the capsule sleeve, produced a hydrous rhyolitic melt with dissolved H2S and CH4 (Li et al. 2021). The resulting fO2 estimate is significantly more reduced than that for the magnetite-wüstite (MW)-buffered experiment where H2S and CH4 were undetected (Li et al. 2021), possibly to the extent of the quartz-iron-fayalite (QIF) buffered conditions produced when BN is used as a capsule or crucible (Wendlandt et al. 1982). To establish an explanation for such a discrepancy, we have conducted further investigation to better constrain the fO2 imposed by BN, when used as a capsule sleeve. Here we report results on analyses of Fe content in Au capsules, a comparative experiment using a QIF buffer and an experiment with an Fe-(Mg,Fe) O sensor for direct analysis of fO2. The calibration of the equilibrium between FeO in melt and Fe in the Au capsule, from Ratajeski and Sisson (1999) appears to be inadequate in constraining fO2 for our experiments. However, we were able to obtain Fe diffusion coefficients in Au from the Fe diffusion profiles observed in the capsule of the Fe-(Mg,Fe)O sensor experiment, and both the inner and outer capsules of the MW-buffered experiment, with resulting values of 1 × 10–13 m2/s, 3 × 10–14 m2/s, and 5 × 10–14 m2/s, respectively. The QIF-buffered and Fe-(Mg,Fe)O sensor experiments provide several lines of evidence supporting the observation that BN imposes QIF-like redox conditions. First, the Fe-(Mg,Fe)O sensor returned an fO2 value of QIF. Second, the “apparent” partition coefficients between FeO content in melt and Fe in the Au capsules are similar between the BN experiment and the QIF-buffered experiment. Third, we observe CH4 and H2O peaks with similar intensities in the Raman spectra of melts from these two experiments, suggesting similar H2 and thus O2 fugacity. As our experiments were performed on a cubic press with the experimental assembly encased in a pyrophyllite cube, we interpret that the significantly reduced conditions imposed by BN are likely due to high H2O activity maintained by dehydration of pyrophyllite, which can be explained using the reaction 2BN + 3H2O = B2O3 + N2 + 3H2. Lower H2O activity will reduce or inhibit the oxidation of BN and its fO2 buffering ability. If heat-treated, BN acts as a highly efficient H2 barrier, as shown by Truckenbrodt et al. (1997). Through our efforts to determine the fO2 imposed by using BN as a capsule sleeve in our experimental assembly, we are able to demonstrate the reducing ability of BN as an assembly component and, furthermore, shed light on the process by which BN imposes such reduced fO2. We hereby present what we have learned during the course of this investigation in the hope that the effect of BN on fO2 control is both recognized and further exploited in future experimental studies.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Speciation and transport properties of supercritical fluids is critical for understanding their behavior in the Earth’s interior. Here, we report a systematic first principles molecular dynamics simulation study of the structure, speciation, self-diffusivity (D), and viscosity (η) of SiO2 melt, NaAlSi3O8 melt, SiO2-H2O and NaAlSi3O8-H2O fluids at 2000–3500 K with 0–70 wt% H2O. Our calculations show that as the water content increases, the proportion of Q0 species (Qn species, where n is the number of bridging oxygens in an individual Si/Al-O polyhedra) increases while Q4 decreases. The proportions of Q1, Q2, and Q3 species first increase and then decrease with increasing water content. The diffusivity sequence for the supercritical SiO2-H2O fluids is DH &amp;gt;DO &amp;gt;DSi, and for the supercritical NaAlSi3O8-H2O fluids, on the whole, is DNa ≈ DH &amp;gt;DO &amp;gt;DAl ≈ DSi. The viscosities of the two systems decrease drastically at the beginning of the increase in water content, and then decrease slowly. We demonstrate that the exponential decrease in the viscosity of polymerized silicate melt with increasing water content is due to a sharp decrease in the proportion of Q4 species and increase in Si-O-H. The typical structural feature of supercritical fluid is that it contains a large amount of easy-to-flow partially polymerized or depolymerized protonated silicate units, which leads to a low viscosity while being enriched in silicate. This feature provides supercritical fluids the potential to transport elements that are hard to migrate in aqueous fluids or hydrous silicate melts, such as high field strength elements.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Clay-mineral evolution in supergene environments is commonly a complex process subject to hydrologic influences on clay-mineral transformations, yet these influences remain insufficiently investigated to date. A quaternary red soil profile with evident redoximorphic features in subtropical monsoonal China was investigated with a focus on processes of secondary clay-mineral transformation. Evidence provided by soil physical and chemical descriptions, clay-mineral analysis, spectroscopic characterization, extractions of pedogenic Al and Fe species, and geochemical compositions reveals a complex relationship of clay minerals and iron phases to pedogenic weathering conditions as a function of depth in the studied soil profile. The soil profile can be divided into a homogenous horizon (HH; 0–2.0 m), a redoximorphic horizon (RH; 2.0–6.0 m), and a basal layer (BL; 6.0–7.2 m), and these three horizons are dominated by various intermediate clay phases. The HH is characterized by moderately acidic conditions (mean pH = 5.2) and low total organic content (TOC; TOC ≤2.1 g kg–1). More importantly, compared with the lower horizons, the HH contains significantly more active acid-forming cations, as reflected by a greater abundance of Al phases and higher aluminum saturation levels. We infer that the occurrence of hydroxy-interlayered vermiculite (HIV) in the HH is tightly coupled with the nature of the soil acidic pools, which include both H+ ions (i.e., pH) and active acid-forming cations (e.g., Al3+ and Fe3+). The reaction pathway from primary minerals to final weathering products appears to be highly sensitive to dynamic hydrological processes. HIV is favored in generally oxic, well-drained soil systems with adequate acidic cations to maintain acidic weathering. When soils are more waterlogged and the aqueous solution is dominated by base cations, primary minerals tend to transform to smectite group minerals. Therefore, discrete smectite, interstratified illite-smectite (I-S), and interstratified kaolinite-smectite (K-S) were observed only in the RH and BL. We present a novel framework that links clay-mineral transformation pathways to soil hydrological disturbances, providing new insights into understanding the kinetics of water-mineral interactions in natural soil systems.</jats:p>