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Abstract In this study, we investigated an unusual natural Mn oxide hollandite-group mineral from the Kohare Mine, Iwate Prefecture, Japan, that has predominantly water molecules in the tunnels, with K, Na, Ca, and Ba. The specimens are labeled as type manjiroite, but our analyses show that Na is not the dominant tunnel species, nor is it even the primary tunnel cation, suggesting either an error in the original analyses or significant compositional variation within samples from the type locality. Chemical analyses, X-ray photoelectron spectroscopy, and thermal gravimetric analysis measurements combined with Rietveld refinement results using synchrotron X-ray powder diffraction data suggest the chemical formula: (K0.19Na0.17Ca0.03Ba0.01H2O1.60)(Mn5.024+Mn2.823+Al0.14Fe0.02)O13.47(OH)2.53. Our analyses indicate that water is the primary tunnel species, and although water has been reported as a component in natural hollandites, this is the first detailed study of the crystal structure and dehydration behavior of a natural hydrous hollandite with water as the predominant tunnel species. This work underscores the rarity of natural Na-rich hollandite phases and focuses new attention on the role of hydrous components of hollandite-like phases in determining their capacities to exchange or accommodate various cations, such as Li+, Na+, Ba2+, Pb2+, and K+ in natural systems. 

Corals nucleate and grow aragonite crystals, organizing them into intricate skeletal structures that ultimately build the world’s coral reefs. Crystallography and chemistry have profound influence on the material properties of these skeletal building blocks, yet gaps remain in our knowledge about coral aragonite on the atomic scale. Across a broad diversity of shallow-water and deep-sea scleractinian corals from vastly different environments, coral aragonites are remarkably similar to one another, confirming that corals exert control on the carbonate chemistry of the calcifying space relative to the surrounding seawater. Nuances in coral aragonite structures relate most closely to trace element chemistry and aragonite saturation state, suggesting the primary controls on aragonite structure are ionic strength and trace element chemistry, with growth rate playing a secondary role. We also show how coral aragonites are crystallographically indistinguishable from synthetic abiogenic aragonite analogs precipitated from seawater under conditions mimicking coral calcifying fluid. In contrast, coral aragonites are distinct from geologically formed aragonites, a synthetic aragonite precipitated from a freshwater solution, and mollusk aragonites. Crystallographic signatures have future applications in understanding the material properties of coral aragonite and predicting the persistence of coral reefs in a rapidly changing ocean.

 

Abstract Raman spectra were collected for an extensive set of well-characterized layer-structure Mn oxide mineral species (phyllomanganates) employing a range of data collection conditions. We show that the application of various laser wavelengths, such as 785, 633, and 532 nm, at low power levels (30–500 μW) in conjunction with the comprehensive database of standard spectra presented here, makes it possible to distinguish and identify the various phyllomanganate minerals. The Raman mode relative intensities can vary significantly as a function of crystal orientation relative to the incident laser light polarization direction as well as incident laser light wavelength. Consequently, phase identification success is enhanced when using a standards database that includes multiple spectra collected for different crystal orientations and with different laser light wavelengths. The position of the highest frequency Raman mode near 630–665 cm–1 shows a strong linear correlation with the fraction of Mn3+ in the octahedral Mn sites. With the comprehensive Raman database of well-characterized Mn oxide standards provided here (and available online as Online Material1), and use of appropriate data collection conditions, micro-Raman is a powerful tool for identification and characterization of biotic and abiotic Mn oxide phases from diverse natural settings, including on other planets, as well as for laboratory and industrial materials. 

Abstract Water can be stored in nominally anhydrous minerals as substitutional hydroxyl, generating vast but commonly unrecognized H2O reservoirs in ostensibly dry regimes. Researchers have long known that hematite (α-Fe2O3) can accommodate small concentrations of hydroxyl through the substitution of Fe3+ by 3H+. Our study of natural hematite has demonstrated the occurrence of “hydrohematite” phases that are 10–20 mol% deficient in Fe and accordingly contain 3.6–7.8 mol% structural water. Intergrown with natural hydrohematite samples were superhydrous goethite-like phases exhibiting an Fe deficiency of 10–20 mol% relative to end-member goethite (α-FeOOH). We synthesized hydrohematite in alkaline solutions (pH 9–12) at low temperatures (T < 200 °C) using fresh ferrihydrite as the transient precursor, and we observed a nonclassical crystallization pathway involving vacancy inoculation by Fe as nanocrystals evolved. The high level of incorporation of H2O in iron (hydr)oxides dramatically alters their behaviors as catalysts and pigments, and the presence of hydrohematite in rocks may rule out high-T diagenesis. We propose that hydrohematite is common in low-T occurrences of Fe oxide on Earth, and by extension it may inventory large quantities of water in apparently arid planetary environments, such as the surface of Mars. 

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. 

Abstract Raman spectra were collected for an extensive set of well-characterized tunnel-structure Mn oxide mineral species employing a range of data collection conditions. Using various laser wavelengths, such as 785, 633, and 532 nm at low power levels (30–500 µW), as well as the comprehensive database of standard spectra presented here, it is generally possible to distinguish and identify the various tunnel structure Mn oxide minerals. The Raman mode relative intensities can vary significantly as a function of crystal orientation relative to the incident laser light polarization direction as well as laser light wavelength. Consequently, phase identification success is enhanced when using a standards database that includes multiple spectra collected for different crystal orientations and with different laser light wavelengths. For the hollandite-group minerals, the frequency of the Raman mode near 630 cm–1 shows a strong linear correlation with the fraction of Mn3+ in the octahedral Mn sites. With the comprehensive Raman database of well-characterized Mn oxide standards provided here (and available online as Supplemental Materials1), and use of appropriate data collection conditions, micro-Raman is a powerful tool for identification and characterization of biotic and abiotic Mn oxide phases from diverse natural settings, including on other planets.