Control over phase separation and nucleation using a laser-tweezing potential

Control over the nucleation of new phases is highly desirable but elusive. Even though there is a long history of crystallization engineering by varying physicochemical parameters, controlling which polymorph crystallizes or whether a molecule crystallizes or forms an amorphous precipitate is still a poorly understood practice. Although there are now numerous examples of control using laser-induced nucleation, the absence of physical understanding is preventing progress. Here we show that the proximity of a liquid–liquid critical point or the corresponding binodal line can be used by a laser-tweezing potential to induce concentration gradients. A simple theoretical model shows that the stored electromagnetic energy of the laser beam produces a free-energy potential that forces phase separation or triggers the nucleation of a new phase. Experiments in a liquid mixture using a low-power laser diode confirm the effect. Phase separation and nucleation using a laser-tweezing potential explains the physics behind non-photochemical laser-induced nucleation and suggests new ways of manipulating matter

Hypogene Caves of the Tasmanic Karsts of Eastern Mainland Australia

The Tasmanic karsts of eastern Australia extend from the south-eastern tip of Tasmania to the far north of Queensland. The mainland section incorporating the eastern parts of Victoria, New South Wales and Queensland contains more than one hundred and twenty bodies of cavernous Palaeozoic limestone, most of which form impounded karsts. Many of these karst areas are small, difficult to access, contain a small number of caves and have received little attention from cavers and even less attention from scientists. Some 21 karst areas stand out for their number of caves and their diversity of underground features. Almost all of the Tasmanic caves in mainland Australia show a high degree of structural guidance and are developed in massive high-purity limestone. Solution dolines are rare or absent in the surrounding karst. Some caves appear to have been formed entirely by a single hypogenic event while others have been modified by several hypogenic events (multiphase caves). In other caves, hypogene forms have been overprinted by later epiphreatic, paragenetic, fluvial and breakdown events (multiphase/multiprocess caves). Where there are active rivers in the caves, the rivers are often much smaller than the cavities they flow through, take complex paths through the rock and are captured into pre-existing cavities. The evidence for a hypogene origin of these caves is largely morphological, but is supported by circumstantial evidence such as intersection of palaeokarst, proximity to regional faults and tenuous relationships with the surrounding geomorphology and hydrology

Thermal stability of crandallite CaAl3(PO4)2(OH)5.(H2O) A 'Cave' mineral from the Jenolan Caves

Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral crandallite CaAl3(PO4)2(OH)5•(H2O) and to ascertain the thermal stability of this ‘cave’ mineral. X-ray diffraction proves the presence of the mineral and identifies the products after thermal decomposition. The mineral crandallite is formed through the reaction of calcite with bat guano. Thermal analysis shows that the mineral starts to decompose through dehydration at low temperatures at around 139°C while dehydroxylation occurs over the temperature range 200 to 700°C with loss of OH units. The critical temperature for OH loss is around 416°C and above this temperature the mineral structure is altered. Some minor loss of carbonate impurity occurs at 788°C. This study shows the mineral is unstable above 139°C. This temperature is well above the temperature in caves, which have a maximum temperature of 15°C. A chemical reaction for the synthesis of crandallite is offered and the mechanism for the thermal decomposition is given

Thermal stability of the 'cave' mineral ardealite Ca2(HPO4)(SO4).4H2O

Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral ardealite and to ascertain the thermal stability of this ‘cave’ mineral. The mineral ardealite Ca2(HPO4)(SO4)•4H2O is formed through the reaction of calcite with bat guano. The mineral shows disorder and the composition varies depending on the origin of the mineral. Thermal analysis shows that the mineral starts to decompose over the temperature range 100 to 150°C with some loss of water. The critical temperature for water loss is around 215°C and above this temperature the mineral structure is altered. It is concluded that the mineral starts to decompose at 125°C, with all waters of hydration being lost after 226°C. Some loss of sulphate occurs over a broad temperature range centred upon 565°C. The final decomposition temperature is 823°C with loss of the sulphate and phosphate anions

Minerals of Jenolan Caves, New South Wales, Australia: Geological and biological interactions

Volume: 136Start Page: 1End Page: 1

River–groundwater connectivity in a karst system, Wellington, New South Wales, Australia

The characterization of river–aquifer connectivity in karst environments is difficult due to the presence of conduits and caves. This work demonstrates how geophysical imaging combined with hydrogeological data can improve the conceptualization of surface-water and groundwater interactions in karst terrains. The objective of this study is to understand the association between the Bell River and karst-alluvial aquifer at Wellington, Australia. River and groundwater levels were continuously monitored, and electrical resistivity imaging and water quality surveys conducted. Two-dimensional resistivity imaging mapped the transition between the alluvium and karst. This is important for highlighting the proximity of the saturated alluvial sediments to the water-filled caves and conduits. In the unsaturated zone the resistivity imaging differentiated between air- and sediment-filled karst features, and in the saturated zone it mapped the location of possible water- and sediment-filled caves. Groundwater levels are dynamic and respond quickly to changes in the river stage, implying that there is a strong hydraulic connection, and that the river is losing and recharging the adjacent aquifer. Groundwater extractions (1,370 ML, megalitres, annually) from the alluvial aquifer can cause the groundwater level to fall by as much as 1.5 m in a year. However, when the Bell River flows after significant rainfall in the upper catchment, river-leakage rapidly recharges the alluvial and karst aquifers. This work demonstrates that in complex hydrogeological settings, the combined use of geophysical imaging, hydrograph analysis and geochemical measurements provide insights on the local karst hydrology and groundwater processes, which will enable better water-resource and karst management

Suppression of glucan, water dikinase in the endosperm alters wheat grain properties, germination and coleoptile growth

Summary: Starch phosphate ester content is known to alter the physicochemical properties of starch, including its susceptibility to degradation. Previous work producing wheat (Triticum aestivum) with down-regulated glucan, water dikinase, the primary gene responsible for addition of phosphate groups to starch, in a grain-specific manner found unexpected phenotypic alteration in grain and growth. Here, we report on further characterization of these lines focussing on mature grain and early growth. We find that coleoptile length has been increased in these transgenic lines independently of grain size increases. No changes in starch degradation rates during germination could be identified, or any major alteration in soluble sugar levels that may explain the coleoptile growth modification. We identify some alteration in hormones in the tissues in question. Mature grain size is examined, as is Hardness Index and starch conformation. We find no evidence that the increased growth of coleoptiles in these lines is connected to starch conformation or degradation or soluble sugar content and suggest these findings provide a novel means of increasing coleoptile growth and early seedling establishment in cereal crop species