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.     

Runoff generation mechanisms in pastures of the Sand Mountain region of Alabama—a field investigation

Excessive application of poultry litter to pastures in the Sand Mountain region of north Alabama has resulted in phosphorus (P) contamination of surface water bodies and buildup of P in soils of this region. Since surface runoff is recognized as the primary mechanism of P transport, understanding surface runoff generation mechanisms are crucial for alleviating water quality problems in this region. Identification of surface runoff generation mechanisms is also important for delineation of hydrologically active areas (HAAs). Therefore, the specific objective of this study was to identify surface runoff generation mechanisms (infiltration excess versus saturation excess) using distributed surface and subsurface sensors and rain gauge. Results from three rainfall events (2·13–3·43 cm) of differing characteristics, and sensor data at four locations with differing soil hydraulic properties along the hillslope showed that the main surface runoff generation mechanism in this region is infiltration excess. Because of this, rainfall intensity and soil hydraulic conductivity were found to play dominant roles in surface runoff generation in this region. Further, only short periods of a few rainfall events during which the rainfall intensity is high produce surface runoff. This study indicates that perhaps subsurface flows and transport of P in subsurface flows need to be quantified to reduce P contamination of surface water bodies in this region. Current studies at this location are identifying spatial and temporal distribution of HAAs, quantifying rainfall characteristics that generate runoff, and estimating runoff volume that results from connected HAAs. Copyright © 2008 John Wiley & Sons, Ltd.     

Topographic, geologic and cavity effects on the harmonic content of tidal strain

Summary. The combined effects of topography, geology and cavities upon the measurements of tidal strains are considered. A theoretical model is proposed in which the topography and geology are modelled with finite elements, and the cavity (assumed to be elliptical) modelled using the analytical theory. The three effects are then superimposed to form a total model. Previous experimental results obtained for the solid tidal strain in Eastern Australia (Blair & Sydenham) are compared with the present theoretical model and reasonable agreement is found assuming values of the Love numbers for the Gutenberg—Bullen A earth model in which h = 0.61 and l = 0.08 (Farrell). Further experimental results are presented for two strain meters, only one of which is not significantly influenced by the cavity. The relative difference, in harmonic content between the recordings of both strain meters is compared with that predicted by the theoretical model.     

Relaxation Oscillations in Tidally Evolving Satellites

We study the rotational evolution under tidal torques of axisymmetric natural satellites in inclined, precessing orbits. In the spin- and orbit-averaged equations of motion, we find that a global limit cycle exists for parameter values near the stability limit of Cassini state . The limit cycle involves an alternation between states of near-synchronous spin at low obliquity, and strongly subsynchronous spin at an obliquity near 90°. This dynamical feature is characterized as a relaxation oscillation, arising as the system slowly traverses two saddle-node bifurcations in a reduced system. This slow timescale is controlled by ε, the nondimensional tidal dissipation rate. Unfortunately, a straightforward expansion of the governing equations for small ε is shown to be insufficient for understanding the underlying structure of the system. Rather, the dynamical equations of motion possess a singular term, multiplied by ε, which vanishes in the unperturbed system. We thus provide a demonstration that a dissipatively perturbed conservative system can behave qualitatively differently from the unperturbed system. This revised version was published online in July 2006 with corrections to the Cover Date.     

Relative abundance of snapper (Chrysophrys auratus) across habitats within an estuarine system

Many fish species rely on estuarine nursery habitats as they transition to adult life stages. Quantifying nursery value, however, requires identification of the life stages (often small and short-lived) that utilise nursery habitats, and survey methods that provide comparable estimates across habitats. We focused our surveys on post-settlement snapper (Chrysophrys auratus) using video camera deployments across habitats within a northeastern New Zealand harbour. Post-settlement snapper abundance was higher among structured habitat types relative to bare sediments, with the type of structured habitat not influential. The exception appeared to be for reef habitat (although sampling was limited). Reef sites were structurally complex, but largely inhabited by older life stages (snapper and other fish species). Overall, nursery value for snapper appears to be connected to structure, rather than structure type. This result emphasises the importance of a broadened scope to coastal fishery management, one that incorporates not just fish extraction, but also habitat maintenance or restoration.     

Origin of honeycombs and related weathering forms in Oligocene Macigno Sandstone,Tuscan coast near Livorno,Italy

Two types of cavernous‐weathering features are exposed in the Oligocene Macigno Sandstone along 5 km of the Tuscan coast south of Livorno, Italy. Honeycomb cells (type 1 features) are typical closely spaced, more or less circular pits of centimetre scale that have been eroded 2 to 6 cm below the general surface of bedding planes or joints. ‘Aberrant honeycomb’ cells (type 2 features) are highly elongate, polygonal, or irregular ?at depressions of decimetre scale surrounded by walls rarely higher than 2 cm, some of which pass into long, free‐standing walls or tendrils. Thus, not all type 2 ‘honeycomb’ cells are fully enclosed. We measured the geometry of 551 honeycomb cells and examined various rock properties (microscopic texture and fabric, mineralogy, porosity, permeability, and chemical composition) to isolate factors that control the size, shape, distribution, and pattern of the honeycombs. Our goal was to narrow potential origins of the features and to understand their formation. The ubiquitous occurrence of sea salt in the honeycombs and scanning electron microscope evidence of physical weathering of silicates, especially micas, favours an origin for the honeycombs chie?y by salt weathering. Honeycombs do not form in siltstone, iron‐oxide‐impregnated sandstone, calcite‐cemented concretions, or in case‐hardened joints. Thus, salt weathering of type 1 and 2 honeycombs is not effective in very low permeability rocks. We propose for type 1 honeycombs that seawater is drawn into micropores of the sandstone and evolves into self‐organized diffusion cells (Turing patterns). Selective evaporation at the stationary nodes of diffusion cells, which form at the same site over time, leads to the precipitation of salt, then grains spall off, and pits are formed. The deepest pits (>40 mm) formed where Turing patterns consistently formed at the same sites. Although the walls are more porous and weathered than the host sandstone, they become selectively case hardened by an unidenti?ed component of low abundance. Initial honeycomb cell shape and gravity locally in?uenced type 1 honeycomb shapes. We suggest that type 2 honeycombs develop where diffusion‐controlled Turing patterns lead to case‐hardening along linear trends; gravity and rock fabric are important locally in in?uencing the orientation of the walls. Only type 2 cells are forming today, suggesting recent environmental changes. Gravity is not a fundamental control on honeycomb shape; in places it is a contributing factor. Pre‐existing depressions (quarry tool marks) have strongly in?uenced honeycomb shape locally. Copyright © 2004 John Wiley & Sons, Ltd.