Zinc K -edge X-ray absorption near-edge (XANES) spectroscopy was conducted on 40 zinc mineral samples and organic compounds. The K -edge position varied from 9660.5 to 9666.0 eV and a variety of distinctive peaks at higher post-edge energies were exhibited by the materials. Zinc is in the +2 oxidation state in all analyzed materials, thus the variations in edge position and post-edge features reflect changes in zinc coordination. For some minerals, multiple specimens from different localities as well as pure forms from chemical supply companies were examined. These specimens had nearly identical K -edge and post-edge peak positions with only minor variation in the intensity of the post-edge peaks. This suggests that typical compositional variations in natural materials do not strongly affect spectral characteristics. Organic zinc compounds also exhibited a range of edge positions and post-edge features; however, organic compounds with similar zinc coordination structures had nearly identical spectra. Zinc XANES spectral patterns will allow identification of unknown zinc-containing minerals and organic phases in future studies.
more »
« less
Potassium and Calcium K ‐Edge XANES in Chemical Compounds and Minerals: Implications for Geological Phase Identification
Potassium (K) and calcium (Ca)
- Award ID(s):
- 1848153
- NSF-PAR ID:
- 10455499
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Geostandards and Geoanalytical Research
- Volume:
- 44
- Issue:
- 4
- ISSN:
- 1639-4488
- Page Range / eLocation ID:
- p. 805-819
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
In functional materials, the local environment around active species that may contain just a few nearest-neighboring atomic shells often changes in response to external conditions. Strong disorder in the local environment poses a challenge to commonly used extended X-ray absorption fine structure (EXAFS) analysis. Furthermore, the dilute concentrations of absorbing atoms, small sample size and the constraints of the experimental setup often limit the utility of EXAFS for structural analysis. X-ray absorption near-edge structure (XANES) has been established as a good alternative method to provide local electronic and geometric information of materials. The pre-edge region in the XANES spectra of metal compounds is a useful but relatively under-utilized resource of information of the chemical composition and structural disorder in nano-materials. This study explores two examples of materials in which the transition metal environment is either relatively symmetric or strongly asymmetric. In the former case, EXAFS results agree with those obtained from the pre-edge XANES analysis, whereas in the latter case they are in a seeming contradiction. The two observations are reconciled by revisiting the limitations of EXAFS in the case of a strong, asymmetric bond length disorder, expected for mixed-valence oxides, and emphasize the utility of the pre-edge XANES analysis for detecting local heterogeneities in structural and compositional motifs.more » « less
-
more » « less
Abstract Silicate vapors play a key role in planetary evolution, especially dominating early stages of rocky planet formation through outgassed magma ocean atmospheres. Our open-source thermodynamic modeling software “VapoRock” combines the MELTS liquid model with gas-species properties from multiple thermochemistry tables. VapoRock calculates the partial pressures of 34 gaseous species in equilibrium with magmatic liquid in the system Si–Mg–Fe–Al–Ca–Na–K–Ti–Cr–O at desired temperatures and oxygen fugacities (
f O2, or partial pressure of O2). Comparison with experiments shows that pressures and melt-oxide activities (which vary over many orders of magnitude) are reproduced to within a factor of ∼3, consistent with measurement uncertainties. We also benchmark the model against a wide selection of igneous rock compositions including bulk silicate Earth, predicting elemental vapor abundances that are comparable to (Na, Ca, and Al) or more realistic than (K, Si, Mg, Fe, and Ti) those of the closed-source MAGMA code (with maximum deviations by factors of 10–300 for K and Si). Vapor abundances depend critically on the activities of liquid components. The MELTS model underpinning VapoRock was calibrated and extensively tested on natural igneous liquids. In contrast, MAGMA’s liquid model assumes ideal mixtures of a limited set of chemically simplified pseudospecies, which only roughly approximates the nonideal compositional interactions typical of many-component natural silicate melts. Finally, we explore how relative abundances of SiO and SiO2provide a spectroscopically measurable proxy for oxygen fugacity in devolatilized exoplanetary atmospheres, potentially constrainingf O2in outgassed exoplanetary mantles. -
The Alaska Range suture zone exposes Cretaceous to Quaternary marine and nonmarine sedimentary and volcanic rocks sandwiched between oceanic rocks of the accreted Wrangellia composite terrane to the south and older continental terranes to the north. New U-Pb zircon ages, 40Ar/39Ar, ZHe, and AFT cooling ages, geochemical compositions, and geological field observations from these rocks provide improved constraints on the timing of Cretaceous to Miocene magmatism, sedimentation, and deformation within the collisional suture zone. Our results bear on the unclear displacement history of the seismically active Denali fault, which bisects the suture zone. Newly identified tuffs north of the Denali fault in sedimentary strata of the Cantwell Formation yield ca. 72 to ca. 68 Ma U-Pb zircon ages. Lavas sampled south of the Denali fault yield ca. 69 Ma 40Ar/39Ar ages and geochemical compositions typical of arc assemblages, ranging from basalt-andesite-trachyte, relatively high-K, and high concentrations of incompatible elements attributed to slab contribution (e.g., high Cs, Ba, and Th). The Late Cretaceous lavas and bentonites, together with regionally extensive coeval calc-alkaline plutons, record arc magmatism during contractional deformation and metamorphism within the suture zone. Latest Cretaceous volcanic and sedimentary strata are locally overlain by Eocene Teklanika Formation volcanic rocks with geochemical compositions transitional between arc and intraplate affinity. New detrital-zircon data from the modern Teklanika River indicate peak Teklanika volcanism at ca. 57 Ma, which is also reflected in zircon Pb loss in Cantwell Formation bentonites. Teklanika Formation volcanism may reflect hypothesized slab break-off and a Paleocene–Eocene period of a transform margin configuration. Mafic dike swarms were emplaced along the Denali fault from ca. 38 to ca. 25 Ma based on new 40Ar/39Ar ages. Diking along the Denali fault may have been localized by strike-slip extension following a change in direction of the subducting oceanic plate beneath southern Alaska from N-NE to NW at ca. 46–40 Ma. Diking represents the last recorded episode of significant magmatism in the central and eastern Alaska Range, including along the Denali fault. Two tectonic models may explain emplacement of more primitive and less extensive Eocene–Oligocene magmas: delamination of the Late Cretaceous–Paleocene arc root and/or thickened suture zone lithosphere, or a slab window created during possible Paleocene slab break-off. Fluvial strata exposed just south of the Denali fault in the central Alaska Range record synorogenic sedimentation coeval with diking and inferred strike-slip displacement. Deposition occurred ca. 29 Ma based on palynomorphs and the youngest detrital zircons. U-Pb detrital-zircon geochronology and clast compositional data indicate the fluvial strata were derived from sedimentary and igneous bedrock presently exposed within the Alaska Range, including Cretaceous sources presently exposed on the opposite (north) side of the fault. The provenance data may indicate ~150 km or more of dextral offset of the ca. 29 Ma strata from inferred sediment sources, but different amounts of slip are feasible. Together, the dike swarms and fluvial strata are interpreted to record Oligocene strike-slip movement along the Denali fault system, coeval with strike-slip basin development along other segments of the fault. Diking and sedimentation occurred just prior to the onset of rapid and persistent exhumation ca. 25 Ma across the Alaska Range. This phase of reactivation of the suture zone is interpreted to reflect the translation along and convergence of southern Alaska across the Denali fault driven by highly coupled flat-slab subduction of the Yakutat microplate, which continues to accrete to the southern margin of Alaska. Furthermore, a change in Pacific plate direction and velocity at ca. 25 Ma created a more convergent regime along the apex of the Denali fault curve, likely contributing to the shutting off of near-fault extension- facilitated arc magmatism along this section of the fault system and increased exhumation rates.more » « less
-
more » « less
A common characteristic of many “overdoped” cuprates prepared with high-pressure oxygen is
T c values ≥ 50 K that often exceed that of optimally doped parent compounds, despite O stoichiometries that place the materials at the edge or outside of the conventional boundary between superconducting and normal Fermi liquid states. X-ray absorption fine-structure (XAFS) measurements at 52 K on samples of high-pressure oxygen (HPO) YSr2Cu2.75Mo0.25O7.54,T c = 84 K show that the Mo is in the (VI) valence in an unusually undistorted octahedral geometry with predominantly Mo neighbors that is consistent with its assigned substitution for Cu in the chain sites of the structure. Perturbations of the Cu environments are minimal, although the Cu X-ray absorption near-edge structure (XANES) differs from that in other cuprates. The primary deviation from the crystal structure is therefore nanophase separation into Mo- and Cu-enriched domains. There are, however, indications that the dynamical attributes of the structure are altered relative to YBa2Cu3O7, including a shift of the Cu-apical O two-site distribution from the chain to the plane Cu sites. Another effect that would influenceT c is the possibility of multiple bands at the Fermi surface caused by the presence of the second phase and the lowering of the Fermi level.
