XRD, micro-XANES, EMPA, and SIMS investigation on phlogopite single crystals from Mt. Vulture (Italy)
-
F. Scordari
,
M.D. Dyar
Abstract
Selected phlogopite flakes from Mt. Vulture in southern Italy were studied using a combination of single-crystal techniques: electron microprobe analysis (EMPA), secondary ion mass spectrometry (SIMS), single-crystal X-ray diffraction (SCXRD), and micro-X-ray absorption near-edge spectroscopy (XANES). The latter technique was employed to analyze the structure of the Fe-K absorption edge over the region from 7080-8100 eV and to determine Fe3+/∑Fe at a micrometer scale, albeit with large error bars due to known effects of orientation on pre-edge energy.
The annite component, Fe/(Mg-i-Fe), of the samples studied ranged from 0.16 to 0.31, the Ti content from 0.11 to 0.27 atoms per formula unit (apfii) and the Ba content from 0.03 to 0.09 apfu. SIMS analysis showed H2O (wt%) = 1.81-3.30, F (wt%) = 0.44-1.29, and Li2O (wt%) = 0.001-0.027. The intra single-crystal chemical variability for major/minor elements (Mg, Fe, Al, Ba, Ti, and K) was found particularly significant for samples VUT191_11 and PG5_1, less significant for the other samples of the set. SIMS data relative to crystals VUT187_24, VUT191_10, VUT191_11, and VUT187_28 showed a noteworthy variation in the concentrations of some light elements (H, Li, and F) with coefficient of variation CV (as 1σ%) up to -18% for H2O.
The analyzed micas belong to the 1M polytype. Structure refinements using anisotropic displacement parameters were performed in space group Clim and converged at 3.08 <R < 3.63,3.32 <RW < 3.98%. Micro-XANES results yielded Fe3+/£Fe from 51-93%. Previous Mossbauer data from powdered samples suggested Fe3+/∑Fe values ranging from 49-87%. However, the Fe3+ content determined by both techniques is sometimes remarkably different, in part because of the large errors (±10-15%) presently associated with the micro-XANES technique and m part because the Fe3+ content of a single crystal may significantly depart from the average value obtamed from routine Mossbauer analysis.
The combination of EMPA, SIMS, and micro-XANES resulted in the characterization of the samples at a comparable spatial scale. By means of in-situ data and the results of crystallographic investigations, the occurrence of different relative amounts of M3*-oxy [VIM2+ + (OH)- ↔ VIM3+ + O2- + ½H2↑], Ti-oxy substitutions [VIM2+ + 2(OH)- ↔VITi4+ + 2O2- + H2↑], and Ti-vacancy (⃞) substitution (2VIM2+ ↔ + VITi4+ + VI⃞) was ascertained for the studied samples.
© 2015 by Walter de Gruyter Berlin/Boston
Articles in the same Issue
- Characterization of cation environments in polycrystalline forsterite by 25Mg MAS, MQMAS, and QCPMG NMR
- Structure of nanocrystalline phyllomanganates produced by freshwater fungi
- First-principles study on variation of lattice parameters of mullite Al4+2xSi2–2xO10–x (x = 0.125, 0.250, 0.375)
- Natrolite may not be a “soda-stone” anymore: Structural study of fully K-, Rb-, and Cs-exchanged natrolite
- Metal retention, mineralogy, and design considerations of a mature permeable reactive barrier (PRB) for acidic mine water drainage in Northumberland, U.K.
- A relationship between d104 value and composition in the calcite-disordered dolomite solid-solution series
- XRD, micro-XANES, EMPA, and SIMS investigation on phlogopite single crystals from Mt. Vulture (Italy)
- Volume behavior of the 10 Å phase at high pressures and temperatures, with implications for H2O content
- Interfacial tension between immiscible liquids in the system K2O-FeO-Fe2O3-Al2O3-SiO2 and implications for the kinetics of silicate melt unmixing
- H2O and the dehydroxylation of phyllosilicates: An infrared spectroscopic study
- Effects of intermediate range structure on the 29Si NMR chemical shifts of framework silicates: Results for analcime
- High-temperature Mössbauer spectroscopy: A probe for the relaxation time of Fe species in silicate melts and glasses
- The thermal equation of state of FeTiO3 ilmenite based on in situ X-ray diffraction at high pressures and temperatures
- OH species, U ions, and CO/CO2 in thermally annealed metamict zircon (ZrSiO4)
- Crystallographic and chemical constraints on the nature of the proustite–pyrargyrite solid-solution series
- Accurate μRaman characterization of reaction products at the surface of (bio)oxidized pyrite
- Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy
- AFM study of the epitaxial growth of brushite (CaHPO4·2H2O) on gypsum cleavage surfaces
- Compressibility of protoamphibole: A high-pressure single-crystal diffraction study of protomangano-ferro-anthophyllite
- Crystal structure of hydrous wadsleyite with 2.8% H2O and compressibility to 60 GPa
- Dehydration and rehydration processes in gmelinite: An in situ X-ray single-crystal study
- Characteristics of emission centers in alkali feldspar: A new approach by using cathodoluminescence spectral deconvolution
- Mechanism of metamorphic zircon growth in a granulite-facies quartzite, Adirondack Highlands, Grenville Province, New York
- Speciation and mixing behavior of silica-saturated aqueous fluid at high temperature and pressure
- A critical comment on Thy et al. (2009b): Liquidus temperatures of the Skaergaard magma
Articles in the same Issue
- Characterization of cation environments in polycrystalline forsterite by 25Mg MAS, MQMAS, and QCPMG NMR
- Structure of nanocrystalline phyllomanganates produced by freshwater fungi
- First-principles study on variation of lattice parameters of mullite Al4+2xSi2–2xO10–x (x = 0.125, 0.250, 0.375)
- Natrolite may not be a “soda-stone” anymore: Structural study of fully K-, Rb-, and Cs-exchanged natrolite
- Metal retention, mineralogy, and design considerations of a mature permeable reactive barrier (PRB) for acidic mine water drainage in Northumberland, U.K.
- A relationship between d104 value and composition in the calcite-disordered dolomite solid-solution series
- XRD, micro-XANES, EMPA, and SIMS investigation on phlogopite single crystals from Mt. Vulture (Italy)
- Volume behavior of the 10 Å phase at high pressures and temperatures, with implications for H2O content
- Interfacial tension between immiscible liquids in the system K2O-FeO-Fe2O3-Al2O3-SiO2 and implications for the kinetics of silicate melt unmixing
- H2O and the dehydroxylation of phyllosilicates: An infrared spectroscopic study
- Effects of intermediate range structure on the 29Si NMR chemical shifts of framework silicates: Results for analcime
- High-temperature Mössbauer spectroscopy: A probe for the relaxation time of Fe species in silicate melts and glasses
- The thermal equation of state of FeTiO3 ilmenite based on in situ X-ray diffraction at high pressures and temperatures
- OH species, U ions, and CO/CO2 in thermally annealed metamict zircon (ZrSiO4)
- Crystallographic and chemical constraints on the nature of the proustite–pyrargyrite solid-solution series
- Accurate μRaman characterization of reaction products at the surface of (bio)oxidized pyrite
- Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy
- AFM study of the epitaxial growth of brushite (CaHPO4·2H2O) on gypsum cleavage surfaces
- Compressibility of protoamphibole: A high-pressure single-crystal diffraction study of protomangano-ferro-anthophyllite
- Crystal structure of hydrous wadsleyite with 2.8% H2O and compressibility to 60 GPa
- Dehydration and rehydration processes in gmelinite: An in situ X-ray single-crystal study
- Characteristics of emission centers in alkali feldspar: A new approach by using cathodoluminescence spectral deconvolution
- Mechanism of metamorphic zircon growth in a granulite-facies quartzite, Adirondack Highlands, Grenville Province, New York
- Speciation and mixing behavior of silica-saturated aqueous fluid at high temperature and pressure
- A critical comment on Thy et al. (2009b): Liquidus temperatures of the Skaergaard magma
