Search NASA⌕ Search

SEARCH · Search NASA

Results for “Nesosilicates”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

2 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

X-ray absorption spectroscopy study of Mn reference compounds for Mn speciation in terrestrial surface environments

Abstract X-ray absorption spectroscopy (XAS) offers great potential to identify and quantify Mn species in surface environments by means of linear combination fit (LCF), fingerprint, and shell-fit analyses of bulk Mn XAS spectra. However, these approaches are complicated by the lack of a comprehensive and accessible spectrum library. Additionally, molecular-level information on Mn coordination in some potentially important Mn species occurring in soils and sediments is missing. Therefore, we investigated a suite of 32 natural and synthetic Mn reference compounds, including Mn oxide, oxyhydroxide, carbonate, phosphate, and silicate minerals, as well as organic and adsorbed Mn species, by Mn K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The ability of XAS to infer the average oxidation state (AOS) of Mn was assessed by comparing XANES-derived AOS with the AOS obtained from redox titrations. All reference compounds were studied for their local (<5 Å) Mn coordination environment using EXAFS shell-fit analysis. Statistical analyses were employed to clarify how well and to what extent individual Mn species (groups) can be distinguished by XAS based on spectral uniqueness. Our results show that LCF analysis of normalized XANES spectra can reliably quantify the Mn AOS within ~0.1 v.u. in the range +2 to +4. These spectra are diagnostic for most Mn species investigated, but unsuitable to identify and quantify members of the manganate and Mn(III)-oxyhydroxide groups. First-derivative XANES fingerprinting allows the unique identification of pyrolusite, ramsdellite, and potentially lithiophorite within the manganate group. However, XANES spectra of individual Mn compounds can vary significantly depending on chemical composition and/or crystallinity, which limits the accuracy of XANES-based speciation analyses. In contrast, EXAFS spectra provide a much better discriminatory power to identify and quantify Mn species. Principal component and cluster analyses of k2-weighted EXAFS spectra of Mn reference compounds implied that EXAFS LCF analysis of environmental samples can identify and quantify at least the following primary Mn species groups: (1) Phyllo- and tectomanganates with large tunnel sizes (2 × 2 and larger; hollandite sensu stricto, romanèchite, todorokite); (2) tectomanganates with small tunnel sizes (2 × 2 and smaller; cryptomelane, pyrolusite, ramsdellite); (3) Mn(III)-dominated species (nesosilicates, oxyhydroxides, organic compounds, spinels); (4) Mn(II) species (carbonate, phosphate, and phyllosilicate minerals, adsorbed and organic species); and (5) manganosite. All Mn compounds, except for members of the manganate group (excluding pyrolusite) and adsorbed Mn(II) species, exhibit unique EXAFS spectra that would allow their identification and quantification in mixtures. Therefore, our results highlight the potential of Mn K-edge EXAFS spectroscopy to assess bulk Mn speciation in soils and sediments. A complete XAS-based speciation analysis of bulk Mn in environmental samples should preferably include the determination of Mn valences following the “Combo” method of Manceau et al. (2012), EXAFS LCF analyses based on principal component and target transformation results, as well as EXAFS shell-fit analyses for the validation of LCF results. For this purpose, all 32 XAS reference spectra are provided in the Online Materials1 for further use by the scientific community.

Geochemistry & Geophysics↗
DOE OSTI2023

Gas-mediated trace element incorporation into rhyolite-hosted topaz: A synchrotron microbeam XAS study

Magmatic gas exsolving during late-stage cooling of shallow magmas has been considered an important facilitator of low-pressure alteration and metal transport. However, the chemical properties of such gas, particularly its metal transport mechanisms and capacity, remain elusive. Trace elements in minerals produced by gas-mediated surface reaction or precipitation from gas capture details of gas composition and reaction pathways. However, interpretation of mineral trace element contents is dependent on understanding crystallographic controls on gas/mineral partitioning. Here, this work investigates the structural accommodation of As, Mn, Ga, Ge, Fe, and Ti in vapor-deposited topaz of vesicular topaz rhyolite from the Thomas Range, Utah, through single-crystal synchrotron microbeam X-ray techniques on picogram quantities of those trace elements. X-ray absorption near edge structure (XANES) data indicates that these elements are incorporated into topaz as As 5+ , Fe 3+ , Mn 3+ , Ti 4+ , Ga 3+ , and Ge 4+ . Extended X-ray absorption fine structure (EXAFS) analysis for these trace elements, compared to EXAFS of structural Al and Si, reveals that As 5+ and Ge 4+ are incorporated directly into the tetrahedral site of the topaz structure, with the octahedral site accommodating Mn 3+ , Fe 3+ , Ga 3+ , and Ti 4+ . For As 5+ and Fe 3+ , the structural impact of substitution extends to at least second neighbors (other elements were only resolvable to first neighbors). Further interpretation of the EXAFS results suggests that the substitution of Ti 4+ results in increased distortion of the octahedral site, while the other trace elements induce more uniform expansion correlating in magnitude to their ionic radius. Comparison of quantified X-ray fluorescence (XRF) data for two topaz crystals from this rhyolite reveals variable trace element concentrations for As 5+ , Fe 3+ , Ga 3+ , and Ti 4+ , reflective of a source gas undersaturated in these trace elements changing in concentration over the period of topaz deposition. The identical Ge 4+ content of the two topaz crystals suggests that Ge 4+ in the gas was buffered by the growth of another Ge 4+ -bearing phase, such as quartz. The very low Mn 3+ content in the topaz crystals does not reflect the abundance of Mn 3+ in the gas (saturation of Mn is evidenced by coexisting bixbyite). Instead, it suggests a strong Jahn-Teller inhibitory effect to the substitution of Mn 3+ for Al 3+ in the distorted octahedral site of topaz. It is proposed that exsolution of an HF-enriched gas from cooling rhyolitic magma led to local scouring of Al, Si, and trace metals from the magma. Once topaz crystals nucleated, self-catalyzed reactions that recycle HF led to continued growth of topaz.

36 MATERIALS SCIENCE↗