Si,Al ordering in leucite by high-resolution 27Al MAS NMR spectroscopy

High-resolution ²⁷Al MAS NMR spectra of natural leucite recorded at H ₀=11.7T contain three resolvable resonances at ²⁷Al δ _i = 69.2, 64.7, and 61.0±0.5 ppm. These three resonances are assigned to the three inequivalent framework positions of leucite: T3, T2, and T1, respectively. Fitting the observed spectra yields a Si,Al distribution for leucite in which approximately one-half of the Al is in T1 and one-quarter in each of T2 and T3. This Si,Al distribution differs substantially from those obtained by previous workers using ²⁹Si NMR spectroscopy and X-ray diffraction. New ²⁹Si NMR spectra and revision of previously reported ²⁹Si NMR peak assignments, however, make the ²⁷Al and ²⁹Si NMR results consistent. The ²⁷Al δ _i correlate linearly with the mean T-O-T′ bond angles of the average structure, which allows the peak assignments to be made. However, this correlation lies distinctly toward higher frequency and larger bond angles than correlations for Si,Al ordered aluminosilicates, suggesting that the mean T(Al)-O-T′(Si) bond angle for each site in leucite is smaller than the mean bond angle of the average structure, which is averaged over T(Al)-O-T′(Si) and T(Si)-OT′(Si,Al) angles.     

A plains ceramic clay source characterization by comparative geochemical and petrographic analyses: Results from the Calhan Paint Mines,Colorado, U.S.A.

The Calhan Paint Mines District, 5EP3258, Colorado, presents exposures of an exceptional clay source. When the area also produced prehistoric Ceramic stage sites, it provided the opportunity for both pottery and potential clay source analysis by optical petrography, X‐ray diffraction, and neutron activation. Although the main purpose of this study is the characterization of the ceramics and outcrop clays, results from a limited number of samples suggest that the colorful clays, the figurative “paints,” of the Calhan Paint Mines were purposely used in prehistoric times as clay source materials for ceramic production. The Calhan Paint Mines are quite possibly the only prehistoric Plains Ceramic stage clay source currently confirmed within the state of Colorado. © 2002 Wiley Periodicals, Inc.     

Entropy Analysis of Multiple Scale Causality and Qualitative Causal Shifts in Spatial Systems*

Spatial systems are typically characterized by multiple controlling factors and processes operating at different spatial and temporal scales (multiple scale causality [MSC]). An entropy decomposition‐based approach to MSC is presented here in two contexts. First, given maps or distributions of an observed phenomenon at two or more scales, the contribution at more local or global (relative to the primary scale of observation) controls to the observed entropy can be estimated. Second, a theoretical treatment of the entropy decomposition equations shows that as the range of scale is increased by broadening or narrowing resolutions or by incorporating more controls, the influence of larger or smaller‐scale influences not only changes, but may change qualitatively, e.g., in terms of having positive (entropy‐increasing) or negative (information‐increasing) effects. Such qualitative causal shifts have implications for efforts to use any single causal explanation across the molecular to planetary spatial and instantaneous to geological range of scales relevant to physical geography. The entropy decomposition method is illustrated with an application to soil landscapes in the Ouachita Mountains, Arkansas.     

27Al, 29Si,and 23Na MAS NMR study of an Al,Si ordered alkali feldspar solid solution series

Solid-state ²⁷Al, ²⁹Si and ²³Na MAS NMR spectra have been obtained for an Al,Si ordered low albite to low microcline ion exchange series for which unit-cell parameters and ²⁹Si NMR data have previously been reported. ²⁷Al δ_i vary continuously with composition from 63.4 (±0.5) ppm for albite to 58.9 (±0.5) ppm for microcline, and parallel the ²⁹Si chemical shifts assigned to the T2m-site. The ²⁷Al and ²⁹Si chemical shifts for this series correlate well with composition-dependent lattice parameters, most notably cell volume and the angle [201]¹b. The linewidths of the ²⁹Si and ²⁷Al resonances indicate a significant amount of structural disorder in the intermediate compositions due to Na, K substitution. The 1 σ width of the distribution of average Si-O-T angles for each T-site is estimated to be about 1° for the Or33 sample. The average ²³Na δ_i varies monotonically from -8.5 (±1) ppm for albite to -24.3 (±1)ppm for Or83. Similarly, the average ²³Na nuclear quadrupole coupling constant decreases from 2.60 to 1.15 (±0.05) MHz and the asymmetry parameter of the electric field gradient increases from 0.25 to 0.6 with increasing K-content from albite to Or83. The observed variations in the quadrupole coupling parameters are consistent with simple electrostatic calculations. Higher resolution ²³Na spectra of the intermediate compositions obtained at 11.7 T indicate the presence of an inhomogeneous linebroadening which is related to the distribution of Na-environments. A model based on a random distribution of local compositions does not simulate the spectra, suggesting that the distribution of Na is skewed toward Na-rich clusters. Observation of the ²³Na NMR lineshape of Or49 after short periods of heat treatment indicate that ²³Na NMR is very sensitive to the changes in the Na, K distribution accompanying the early stages of exsolution. Reversible changes occur after heating at 530° C for 3 h, whereas heating at 600° C produces no changes, possibly bracketing the position of the coherent spinodal for Al, Si ordered alkali feldspars at this composition.     

The low-excitation structures of planetary nebulae

The low excitation properties of the planetary nebula (PN) NGC 6720 are known to be unusual, and to imply large ring/core emission ratios. We point out that such characteristics are by no means confined to this source alone, and that high ratios may occur in a large fraction of elliptical and circular PNe. Such trends may arise because of the presence of thin low-excitation emission sheets 'wrapped' within and around the primary outflows. The widths of such shells are required to be exceedingly small, and may (for certain cases) be of order ≪10⁻² pc. Such a mechanism appears capable of explaining most of the observed emission properties, and may arise through shock interaction between differing envelopes. Alternative explanations in terms of bipolar or cylindrical outflows are shown to be implausible.