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1. Effects of pH and Ca exchange on the structure and redox state of synthetic Na-birnessite

   https://doi.org/10.2138/am-2020-7112  

   Elmi, Chiara; Post, Jeffrey E.; Heaney, Peter J.; Ilton, Eugene S. (January 2021, American Mineralogist)

   null (Ed.)

   Abstract Birnessite-like minerals are among the most common Mn oxides in surficial soils and sediments, and they mediate important environmental processes (e.g., biogeochemical cycles, heavy metal confinement) and have novel technological applications (e.g., water oxidation catalysis). Ca is the dominant interlayer cation in both biotic and abiotic birnessites, especially when they form in association with carbonates. The current study investigated the structures of a series of synthetic Ca-birnessite analogs prepared by cation-exchange with synthetic Na-birnessite at pH values from 2 to 7.5. The resulting Ca-exchanged birnessite phases were characterized using powder X-ray diffraction and Rietveld refinement, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning and transmission electron microscopy. All samples synthesized at pH values greater than 3 exhibited a similar triclinic structure with nearly identical unit-cell parameters. The samples exchanged at pH 2 and 3 yielded hexagonal structures, or mixtures of hexagonal and triclinic phases. Rietveld structure refinement and X-ray photoelectron spectroscopy showed that exchange of Na by Ca triggered reduction of some Mn3+, generating interlayer Mn2+ and vacancies in the octahedral layers. The triclinic and hexagonal Ca-birnessite structures described in this study were distinct from Na- and H-birnessite, respectively. Therefore, modeling X-ray absorption spectra of natural Ca-rich birnessites through mixing of Na- and H-birnessite end-members will not yield an accurate representation of the true structure. 

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2. Structure and function of H+/K+ pump mutants reveal Na+/K+ pump mechanisms

   https://doi.org/10.1038/s41467-022-32793-0  

   Young, Victoria C.; Nakanishi, Hanayo; Meyer, Dylan J.; Nishizawa, Tomohiro; Oshima, Atsunori; Artigas, Pablo; Abe, Kazuhiro (December 2022, Nature Communications)

   Abstract Ion-transport mechanisms evolve by changing ion-selectivity, such as switching from Na + to H + selectivity in secondary-active transporters or P-type-ATPases. Here we study primary-active transport via P-type ATPases using functional and structural analyses to demonstrate that four simultaneous residue substitutions transform the non-gastric H + /K + pump, a strict H + -dependent electroneutral P-type ATPase, into a bona fide Na + -dependent electrogenic Na + /K + pump. Conversion of a H + -dependent primary-active transporter into a Na + -dependent one provides a prototype for similar studies of ion-transport proteins. Moreover, we solve the structures of the wild-type non-gastric H + /K + pump, a suitable drug target to treat cystic fibrosis, and of its Na + /K + pump-mimicking mutant in two major conformations, providing insight on how Na + binding drives a concerted mechanism leading to Na + /K + pump phosphorylation. 

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3. Investigation of the crystal structure of a low water content hydrous olivine to 29.9 GPa: A high-pressure single-crystal X-ray diffraction study

   https://doi.org/10.2138/am-2020-7444  

   Xu, Jingui; Fan, Dawei; Zhang, Dongzhou; Li, Bo; Zhou, Wenge; Dera, Przemyslaw K. (December 2020, American Mineralogist)

   null (Ed.)

   Abstract Olivine is the most abundant mineral in the Earth's upper mantle and subducting slabs. Studying the structural evolution and equation of state of olivine at high-pressure is of fundamental importance in constraining the composition and structure of these regions. Hydrogen can be incorporated into olivine and significantly influence its physical and chemical properties. Previous infrared and Raman spectroscopic studies indicated that local structural changes occur in Mg-rich hydrous olivine (Fo ≥ 95; 4883–9000 ppmw water) at high-pressure. Since water contents of natural olivine are commonly <1000 ppmw, it is inevitable to investigate the effects of such water contents on the equation of state (EoS) and structure of olivine at high-pressure. Here we synthesized a low water content hydrous olivine (Fo95; 1538 ppmw water) at low SiO2 activity and identified that the incorporated hydrogens are predominantly associated with the Si sites. We performed high-pressure single-crystal X-ray diffraction experiments on this olivine to 29.9 GPa. A third-order Birch-Murnaghan equation of state (BM3 EoS) was fit to the pressure-volume data, yielding the following EoS parameters: VT0 = 290.182(1) Å3, KT0 = 130.8(9) GPa, and K′T0 = 4.16(8). The KT0 is consistent with those of anhydrous Mg-rich olivine, which indicates that such low water content has negligible effects on the bulk modulus of olivine. Furthermore, we carried out the structural refinement of this hydrous olivine as a function of pressure to 29.9 GPa. The results indicate that, similar to the anhydrous olivine, the compression of the M1-O and M2-O bonds are comparable, which are larger than that of the Si-O bonds. The compression of M1-O and M2-O bonds of this hydrous olivine are comparable with those of anhydrous olivine, while the Si-O1 and Si-O2 bonds in the hydrous olivine are more compressible than those in the anhydrous olivine. Therefore, this study suggests that low water content has negligible effects on the EoS of olivine, though the incorporation of water softens the Si-O1 and Si-O2 bond. 

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4. Halogen Bearing Amphiboles, Aqueous Fluids, and Melts in Subduction Zones: Insights on Halogen Cycle From Electrical Conductivity

   https://doi.org/10.1029/2020JB021339  

   Manthilake, G.; Koga, K. T.; Peng, Y.; Mookherjee, M. (March 2021, Journal of Geophysical Research: Solid Earth)

   Abstract Amphiboles are hydrous minerals that are formed in the oceanic crust via hydrothermal alteration. The partial substitution of halogens for OH⁻makes amphibole one of the principal hosts of Cl and F in the subducting slab. In this study, we investigated the electrical conductivity of a suite of halogen bearing amphibole minerals at 1.5 GPa up to 1,400 K. The discontinuous electrical behavior indicates dehydration of amphibole at ∼915 K. This is followed by dehydration induced hydrous melting at temperatures above 1,070 K. We find that the released aqueous fluids have an electrical conductivity of ∼0.1 S/m. This high electrical conductivity is likely to explain anomalously high electrical conductivity observed in certain subduction zone settings. This high electrical conductivity of an order of magnitude greater than the electrical conductivity of pure aqueous fluids at similar conditions is likely due to the partitioning of the F and Cl into the aqueous fluids. We also noted that subsequent to the dehydration, secondary phases form due to the breakdown of the primary halogen bearing amphibole. Chemical analyses of these secondary phases indicate that they are repositories of F and Cl. Hence, we infer that upon dehydration of the primary halogen bearing amphibole, first the F and Cl are partitioned into the aqueous fluids and then the halogens are partitioned back to the secondary mineral phases. These secondary minerals are likely to transport the halogen to the deep Earth and may in part explain the halogen concentration observed in ocean island basalt. 

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5. Insight into differentiation in alkalic systems: Nephelinite-carbonate-water experiments aimed at Ol Doinyo Lengai carbonatite genesis

   https://doi.org/10.3389/feart.2022.970264  

   Lundstrom, Craig C.; Hervig, Rick; Fischer, Tobias P.; Sivaguru, Mayandi; Yin, Leilei; Zhou, Zhenhao; Lin, Xiaobao; Grossi-Diniz, Rodrigo (September 2022, Frontiers in Earth Science)

   Ol Doinyo Lengai (ODL, Tanzania, East African Rift) is the only known volcano currently erupting carbonatite on Earth with 30 yr. cycles alternating between quiescent carbonatite effusion and explosive, compositionally-zoned silicate eruptions. We performed isothermal crystallization and thermal gradient experiments involving ODL nephelinite, Na 2 CO 3 and H 2 O to understand magmatic differentiation in this system using SEM-EDS x-ray analysis, x-ray tomography, SIMS and LA-ICPMS to characterize samples. Isothermal crystallization experiments document that hydrous liquids coexist with nepheline+feldspar; as peralkalinity increases, temperatures decrease. Presence of Na 2 CO 3 increases the solubility of water in the liquid. Experiments placing nephelinite with H 2 O+ Na 2 CO 3 in a 1,000–350°C thermal gradient show that rapid reaction occurs, resulting in virtually melt-free mineral aggregates having mineral layering reflecting systematic differentiation throughout the capsule. Both types of experiments argue that a continuous interconnected melt exists over a large temperature range in alkalic magmatic systems allowing for differentiation in a reactive mush zone process. Liquid compositions change from carbonate-water bearing nephelinites at high temperature down to hydrous carbonate silicate liquids at <400°C. We propose a model for ODL eruption behavior: 1) nephelinite magmas pond and build a sill complex downward with time; 2) hydrous carbonate melts form in the mush and buoyantly rise, ultimately erupting as natrocarbonatites observed; 3) H 2 O contents build up in melt at the bottom of the sill complex, eventually leading to water vapor saturation and explosive silicate eruptions. The model accounts for eruption cycling and the unusual compositional zoning of ODL silicate tephras. 

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