Relaxation mechanisms and effects of motion in albite (NaAlSi3O8) liquid and glass: A high temperature NMR study

The nuclear magnetic relaxation of ²³Na and ²⁹Si in albite glass and liquid has been studied from 800 K to 1400 K. The dominant spin-lattice relaxation mechanism for ²³Na is found to be nuclear quadrupole interaction arising from the Na⁺ diffusion. The activation energy of the Na diffusion is found to be 71±3 kJ/mol, in close agreement with the results on electrical conductivity and on Na self-diffusion from radio-tracer experiments. The correlation time of the Na motion is estimated to be about 8.5×10^?11 s near the melting point (～1390 K). Both nuclear dipole-dipole interaction and chemical shift anisotropy interaction are large enough to contribute to the ²⁹Si relaxation. However, calculations based on a simplified model which employ single correlation time and exponential correlation function, with interactions typical of crystalline silicates, cannot completely account for the experimental data. NMR relaxation data also reveal that the Si motion is correlated to the Na motion and that the Si is relatively immobile. Several possible motions of SiO₄ tetrahedra that can cause ²⁹Si relaxation are suggested. The motion responsible for ²⁹Si relaxation differs from that which is responsible for viscosity: the apparent activation energy for the former is much lower. Measurements of spin-spin relaxation times and linewidths are also presented and the significance of their temperature dependence is discussed.     

Diffusion and the dynamics of displacive phase transitions in cryolite (Na3AlF6) and chiolite (Na5Al3F14): Multi-nuclear NMR studies

Cryolite is a mixed-cation perovskite (Na₂(NaAl)F₆) which undergoes a monoclinic to orthorhombic displacive phase transition at ～550° C. Chiolite (Na₅Al₃F₁₄) is associated with cryolite in natural deposits, and consists of sheets of corner sharing [AlF₆] octahedra interlayered with edge-sharing [NaF₆] octahedra. Multi-nuclear NMR line shape and relaxation time (T₁) studies were performed on cryolite and chiolite in order to gain a better understanding of the atomic motions associated with the phase transition in cryolite, and Na diffusion in cryolite and chiolite. ²⁷Al, ²³Na, and ¹⁹F static NMR spectra and T₁'s in cryolite suggest that oscillatory motions of the [AlF₆] octahedra among four micro-twin and anti-phase domains in α-cryolite begin at least 150° C below the transition temperature and persist above it. Variable temperature ²³Na MAS NMR further indicates diffusional exchange at a rate of at least 13 kHz between the Na sites by the time the transition temperature is reached. ²⁷Al and ²³Na T₁'s show the same behavior with increasing temperature, indicating the same relaxation mechanisms are responsible for both. The first order nature of the cryolite transition is apparent as a jump in the ²³Na and ²⁷Al T₁'s. Above the transition temperature, the T₁'s decrease slightly indicating that the motions responsible for the drop in T₁, are still present above the transition, further supporting the dynamic nature of the high temperature phase of cryolite. Chiolite ²³Na static spectra decrease in linewidth with increasing temperature, indicating increased Na diffusion, which is interpreted as occurring within the [NaF₆] sheets in the chiolite structure, but not between the two different Na sites. ²⁷Al and ²³Na T₁'s show similar behavior as in cryolite, but there is no discontinuity due to a phase transition. ¹⁹F T₁'s are constant from room temperature to 150° C indicating no oscillatory motion of the [AlF₆] octahedra in chiolite.     

Six-color observations of Algol, 1949–1951

Observations of Algol in six colors, covering both eclipses, are presented. Primary minimum occurred at JD 2433 228.8684.     

Organic carbon content and carbon isotope variations across the Permo-Triassic boundary in the Gartnerkofel-1 borehole,Carnic Alps,Austria

The Gartnerkofel borehole is one of the most thoroughly studied and described Permo-Triassic sections in the world. Detailed bulk organic carbon isotope studies show a negative base shift from ? 24‰ to ? 28‰ in the Latest Permian which latter value persists into the Earliest Triassic after which it decreases slightly to ? 26‰. Two strongly negative peaks of > ? 38‰ in the Latest Permian and a lesser peak of ? 31‰ in the Early Triassic are too negative to be due to a greater proportion of more negative organic matter and must be due to very negative methane effects. The overall change to more negative values across the Bulla/Tesero boundary fits the relative rise in sea level for this transition based on the facies changes. A positive shift in organic carbon isotope values at the Late Permian Event Horizon may be due to an increase in land-derived organic detritus at this level—a feature shown by all Tethyan Permo-Triassic boundary sections though these other sections do not have the same values. Carbonate carbon isotope trends are similar in all sections dropping by 2–3 units across the Permo-Triassic boundary. Gartnerkofel carbonate oxygen values are surprisingly, considering the ubiquitous dolomitization, compatible with values elsewhere and indicate reasonable tropical temperatures of 60 °C in the Latest Permian sabkhas to 20–40 °C in the overlying marine transition beds. Increased land-derived input at the Late Permian Event Horizon may be due to offshore transport by tsunamis whose deposits have been recognized in India at this level.     

Cation field strength effects on high pressure aluminosilicate glass structure: Multinuclear NMR and La XAFS results

We examined aluminosilicate glasses containing a variety of network modifying to intermediate cations (Li, La, Sc, and Fe), quenched from melts at 1 atm to 8 GPa, to further investigate the role of cation field strength in Al coordination changes and densification. ²⁷Al Nuclear Magnetic Resonance Spectroscopy (NMR) reveals that the mean Al coordination increases with increasing pressure in the Li-containing glasses, which can be explained by a linear dependence of fractional change in Al coordination number on cation field strengths in similar K-, Na-, and Ca-containing aluminosilicate glasses (K < Na < Li < Ca). Measured recovered densities follow a similar linear trend. In contrast, the La-containing glasses have significantly lower mean Al coordination numbers at given pressures than the cation field strength of La and glass density would predict. La L₃ X-ray absorption fine structure (XAFS) spectroscopy results indicate a significant increase with pressure in average La-O bond distances, suggesting that La and Al may be “competing” for higher coordinated sites and hence that both play a significant role in the densification of these glasses, especially in the lower pressure range. However, in Na aluminosilicate glasses with small amounts of Sc, ⁴⁵Sc NMR reveals only modest Sc coordination changes, which do not seem to significantly affect the mean Al coordination values. For a Li aluminosilicate glass, ¹⁷O MAS and multiple quantum magic angle spinning (3QMAS) NMR data are consistent with generation of more highly coordinated Al at the expense of non-bridging oxygen (NBO), whereas La aluminosilicate glasses have roughly constant O environments, even up to 8 GPa. Finally, we demonstrate that useful ²³Na and ²⁷Al MAS NMR spectra can be collected for Ca-Na aluminosilicate glasses containing up to 5 wt.% Fe oxide. We discuss the types of structural changes that may accompany density increases with pressure and how these structural changes are affected by the presence of different cations.     

A 29Si MAS NMR study of sub-Tg amorphization of stishovite at ambient pressure

Stishovite, a high-pressure SiO₂ polymorph in which each Si is coordinated by six O atoms, transforms to an amorphous phase when undergoing heat treatment below the glass transition temperature at ambient pressure. We have applied ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR) to study this amorphization process. We found that the amorphous phase generated after heating stishovite for up to 3 days at around 600 ° C consisted exclusively of four-coordinate Si, similar to glasses quenched from melts at ambient pressure. Furthermore, our data suggest that there are subtle structural differences between the amorphous phase transformed from stishovite at 600 ° C and glasses quenched from melts at ambient pressure: the amorphous phase from stishovite had a smaller mean Si-O-Si angle initially, and it gradually relaxed toward the latter with increasing heating time. There was no detectable change in the stishovite structure even after about 80% of it had been converted to the amorphous phase. The mechanism of the amorphization of stishovite is discussed in light of these results.     

Bonding and dynamical phenomena in MgO: A high temperature 17O and 25Mg NMR study

We have measured the isotropic chemical shifts (δ_iso) and the spin-lattice relaxation times (T₁) for ¹⁷O and ²⁵Mg in MgO from room temperature up to 1300° C. The ¹⁷O chemical shifts increase linearly from 47 ppm at room temperature to 57 ppm at 1300° C, and over the same temperature range the ²⁵Mg chemical shift increases linearly from 25 to 27 ppm. These changes are not the result of changes in the bulk magnetic susceptibility of the samples, but may be due to increased orbital overlap which is the result of the increase in thermal vibration of the ions with temperature. In the case of ²⁵Mg, the shift to lower shielding with increasing temperature is opposite to that expected from simple bond length versus chemical shift trends established for the oxides at room temperature. If this is a general phenomenon, high-temperature NMR data may be biased to lower shielding. Spin-lattice relaxation times (T₁) were measured in order to study the energetics of defect motion. T₁'s for ¹⁷O and ²⁵Mg exhibit similar behavior over the range of temperatures studied. Up to 800° C, T₁'s decrease gradually, but above 800° C, T₁'s drop rapidly, with slopes corresponding to apparent activation energies of 192±9 kJ/mol (2.0±0.1 eV) for ¹⁷O and 151±6 kJ/mol (1.56±0.06 eV) for ²⁵Mg. While direct comparison of these activation energies to those derived from diffusion or conductivity measurements is complicated, the similar behavior for both nuclei suggests their relaxation phenomena are related.     

Magic angle spinning NMR observation of sodium site exchange in nepheline at 500° C

Dynamics in minerals at time scales from seconds to microseconds are important in understanding mechanisms of displacive phase transitions, diffusion, and conductivity. High resolution, magic-angle-spinning (MAS) NMR spectroscopy can directly show the rates of exchange among sites, potentially providing less model-dependent information than more traditional NMR relaxation time measurements. Here we use a newly developed high temperature MAS probe (Doty Scientific, Inc.) to observe the exchange of Na⁺ among the alkali sites in a high-Na nepheline at temperatures as high as 500° C. Observed exchange rates are consistent with correlation times derived from cation diffusivity.     

Discriminating sources of PCB contamination in fish on the coastal shelf off San Diego, California (USA)

Management of coastal ecosystems necessitates the evaluation of pollutant loading based on adequate source discrimination. Monitoring of sediments and fish on the shelf off San Diego has shown that some areas on the shelf are contaminated with polychlorinated biphenyls (PCBs). Here, we present an analysis of PCB contamination in fish on the shelf off San Diego designed to discriminate possible sources. The analysis was complicated by the variability of species available for analysis across the shelf, variable affinities of PCBs among species, and non-detects in the data. We utilized survival regression analysis to account for these complications. We also examined spatial patterns of PCBs in bay and offshore sediments and reviewed more than 20 years of influent and effluent data for local wastewater treatment facilities. We conclude that most PCB contamination in shelf sediments and fish is due to the ongoing practice of dumping contaminated sediments dredged from San Diego Bay.