Ferroelastic phase transition in cryolite,Na3AlF6, a mixed fluoride perovskite: High temperature single crystal X-ray diffraction study and symmetry analysis of the transition mechanism

Cryolite, Na₃AlF₆[ = 2Na⁺(Na_0.5 ⁺Al_0.5 ³⁺)F₃] is a mixed fluoride perovskite, in which the corner-sharing octahedral framework is formed by alternating [NaF₆] and [AlF₆] octahedra and the cavities are occupied by Na⁺ ions. At 295 K, it is monoclinic (α phase), space group P2 ₁/n with a = 5.4139 (7), b = 5.6012 (5) and c = 7.7769 (8) Å and β = 90.183 (3)°, Z = 2. A high temperature single crystal X-ray diffraction study in the range 295–900 K indicates a fluctuation-induced first-order phase transition from monoclinic to orthorhombic symmetry at T ₀ ～ 885 K, in contrast to a previous report that it becomes cubic at ～823 K. The space group of the high temperature β phase is Immm with a = 5.632 (4), b = 5.627 (3) and c = 7.958 (4) Å, Z = 2 at 890 K. Above T ₀, the coordination number of the Na⁺ ion in the cavity increases from eight to twelve and the zigzag Na1 — Al octahedral chains parallel to c become straight with the Na1-F-Al angle = 180 °. The phase transition is driven by two coupled primary order parameters. The first corresponds to the rotation of the nearly rigid [AlF₆] group and transforms according to the Γ ₄ ⁺ irreducible representation of Immm. Coupled to the [AlF₆] rotation is a second primary order parameter corresponding to the displacement of the Na2⁺ ion in the cavity from its equilibrium position. This order parameter transforms according to the X ₃ ⁺ irreducible representation of Immm. Following Immm → P2 ₁ /n phase transition, four equivalent domains of P2 ₁/n are determined relative to Immm, which are in an antiphase and/or twin relationship. The abrupt shortening of the octahedral Al-F and Na-F bonds and a sudden change in orientations of the atomic thermal vibration ellipsoids above T ₀ indicate a crossover from displacive to an order-disorder mechanism near the transition temperature. The β phase is interpreted as a dynamic average of four micro-twin and -antiphase domains of the a phase. This view is consistent with the entropy of phase transition, ΔS_trans (11.43 JK^?1 mol^?1) calculated from heat capacity measurements (Anovitz et al. 1987), which corresponds closely to R ln4 (11.53 JK^?1 mol^?1), where 4 is the number of domains formed during the phase transition. The dynamic nature of the β phase is independently confirmed from a considerable narrowing of the ²⁷Al nuclear magnetic resonance (NMR) line-shape above T ₀ (Stebbins et al. 1992).     

Thin surface soil layers attributable to rain-flow transportation on low-angle slopes: An example from semi-arid tropical Queensland,Australia

Particle-size analyses have been made on surface soils and a thin, overlying sandy pavement at 16 sites along a gently sloping transect at Torrens Creek in North Queensland. The transect is 1590 m long and has a maximum gradient of 0.018 (less than 1°). The sandy pavement is enriched in coarse components due to the sorting and differential downslope transport of the finer soil fractions. Particle movement is ascribed to the action of raindrops impacting very shallow, flowing water. The process, referred to as ‘rain-flow transportation’, is active wherever overland flow is too weak to generate rills and channels and occurs in areas of very low slope with permeable surface soils that allow rapid infiltration during storms. Rain-flow transportation is discussed with particular reference to the development of soil profiles in an old, subdued landscape of semi-arid tropical Australia.     

Mineral resources of China: Apparent controls on distribution

This paper attempts to define apparent mineral distribution patterns of China according to tectono-stratigraphic terrane geology. Associations between specific mineral and hydrocarbon deposits and specific tectono-stratigraphic terranes in China suggest that deposits of certain types are spatially constrained by terrane geology. The definition of specific tectono-stratigraphic terranes of China is a valuable initial step in interpreting the geologic history of the nation, although terrane analysis of China is at a very early stage. The recognition that specific deposit types are associated with specific tectono-stratigraphic terranes may make it possible to select appropriate analogues from elsewhere in the world to evaluate China's mineral and hydrocarbon potential. Additionally, understanding the associations between mineral and hydrocarbon deposits and tectono-stratigraphic terranes in China may serve as an aid to future exploration in the nation.     

The helicity constraint in spherical shell dynamos

The motivation for considering distributed large scale dynamos in the solar context is reviewed in connection with the magnetic helicity constraint. Preliminary accounts of 3-dimensional direct numerical simulations (in spherical shell segments) and simulations of 2-dimensional mean field models (in spherical shells) are presented. Interesting similarities as well as some differences are noted. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Could alluvial knickpoint retreat rather than fire drive the loss of alluvial wet monsoon forest,tropical northern Australia?

Drainage rejuvenation through headward migration of alluvial knickpoints is common in ephemeral semi‐arid streams, but has not yet been described for tropical rivers. In the Australian monsoon tropics (AMT), wet monsoon forests have an important ecological function, and are present along many alluvial valleys and springs within a eucalypt‐savanna dominated landscape. Using a combination of LiDAR, remote sensing and field evidence, we observe the ongoing destruction of wet monsoon forest through hydro‐geomorphic feedbacks, along with the headward retreat of an alluvial knickpoint at Wangi Creek in Litchfield National Park, Northern Territory. Due to the highly transmissive shallow aquifer along the lower Wangi Creek, this knickpoint retreat leads to a downstream drop in in‐channel water level, which in turn drives a decrease in the local groundwater table. The lowered groundwater level causes the shallow anabranches and formerly water saturated peaty floodplain soil to desiccate, which results in a reduction of vegetation density. The resulting dry surface conditions allow annual to bi‐annual high frequency low‐intensity fires to affect the monsoon forest, while wet rainforest upstream of the knickpoint remains intact. In this paper, we argue that such hydro‐geomorphic feedbacks may cause the initial destabilization of the forest, which then provides the necessary conditions for the impact of fire. This scenario thus challenges the prevalent view that fire is a first‐order control on the spatial extent of wet monsoonal rainforest in the study area, and provides a new and testable hypothesis for further studies in the AMT. Copyright © 2016 John Wiley & Sons, Ltd.     

Re-colonisation and recovery of populations of dogwhelks Nucella lapillus (L.) on shores formerly subject to severe TBT contamination

Dogwhelks Nucella lapillus became locally extinct on some shores adjacent to areas of high shipping/boating activity during the period of high tributyltin (TBT) contamination in the 1980s and early 1990s. However, the species has now re-colonised sites at which extinction occurred on the Isle of Cumbrae, the northeast coast of England, the Shetland Isles and southwest England. There have also been substantial declines in the severity of imposex on adjacent shores where the species has persisted during this period. Re-colonisation and recovery can be attributed to two measures: regulations prohibiting the use of TBT-based paints on vessels < 25 m in length and the development of slow-releasing, self-polishing copolymer paints. Nevertheless, the International Maritime Organisation has now imposed a total ban on the use of TBT-based paints as antifoulants. This is almost certain to result in the use of paints containing alternative biocides and there is widespread concern that there is relatively little information on which to assess their likely environmental impacts. They could cause substantial environmental damage.     

Deterministically Driven Avalanche Models of Solar Flares

We develop and discuss the properties of a new class of lattice-based avalanche models of solar flares. These models are readily amenable to a relatively unambiguous physical interpretation in terms of slow twisting of a coronal loop. They share similarities with other avalanche models, such as the classical stick–slip self-organized critical model of earthquakes, in that they are driven globally by a fully deterministic energy-loading process. The model design leads to a systematic deficit of small-scale avalanches. In some portions of model space, mid-size and large avalanching behavior is scale-free, being characterized by event size distributions that have the form of power-laws with index values, which, in some parameter regimes, compare favorably to those inferred from solar EUV and X-ray flare data. For models using conservative or near-conservative redistribution rules, a population of large, quasiperiodic avalanches can also appear. Although without direct counterparts in the observational global statistics of flare energy release, this latter behavior may be relevant to recurrent flaring in individual coronal loops. This class of models could provide a basis for the prediction of large solar flares.