Gibbs energies of formation of rare earth oxysulfides

The standard Gibbs energy change accompanying the conversion of rare earth oxides to oxysulfides by reaction of rare earth oxides with diatomic sulfur gas has been measured in the temperature range 870 to 1300 K using the solid state cell: Pt/Cu+Cu2S/R2O2S+R2O3‖(CaO)ZrO2‖Ni+NiO, Pt where R=La, Nd, Sm, Gd, Tb, and Dy. The partial pressure of diatomic sulfur over a mixture of rare earth oxide (R2O3) and oxysulfide (R2O2S) is fixed by the dissociation of Cu2S to Cu in a closed system. The buffer mixture of Cu+Cu2S is physically separated from the rare earth oxide and oxysulfide to avoid complications arising from interaction between them. The corresponding equilibrium oxygen partial pressure is measured with an oxide solid electrolyte cell. Gibbs energy change for the conversion of oxide to the corresponding oxysulfide increases monotonically with atomic number of the rare earth element. Second law enthalpy of formation also shows a similar trend. Based on this empirical trend Gibbs energies of formation of oxysulfides of Pr, Eu, Ho, and Er are estimated as a function of temperature.

What drives plant biodiversity in the clay floodplain grasslands of NSW?

An assessment of the relative influences of management and environment on the composition of floodplain grasslands of north-western New South Wales was made using a regional vegetation survey sampling a range of land tenures (e. g. private property, travelling stock routes and nature reserves). A total of 364 taxa belonging to 55 different plant families was recorded. Partitioning of variance with redundancy analysis determined that environmental variables accounted for a greater proportion (61.3%) of the explained variance in species composition than disturbance-related variables (37.6%). Soil type (and fertility), sampling time and rainfall had a strong influence on species composition and there were also east-west variations in composition across the region. Of the disturbance-related variables, cultivation, stocking rate and flooding frequency were all influential. Total, native, forb, shrub and subshrub richness were positively correlated with increasing time since cultivation. Flood frequency was positively correlated with graminoid species richness and was negatively correlated with total and forb species richness. Site species richness was also influenced by environmental variables (e. g. soil type and rainfall). Despite the resilience of these grasslands, some forms of severe disturbance (e. g. several years of cultivation) can result in removal of some dominant perennial grasses (e. g. Astrebla spp.) and an increase in disturbance specialists. A simple heuristic transitional model is proposed that has conceptual thresholds for plant biodiversity status. This knowledge representation may be used to assist in the management of these grasslands by defining four broad levels of community richness and the drivers that change this status.

Queensland Coastal Wetland Resources: the Northern Territory Border to Flinders River

Protection of coastal wetland environments is an important prerequisite to effective and sustainable fisheries management and conservation of habitats for the use of future generations. Mangroves, saltmarshes and seagrasses directly support local and offshore fisheries through the provision of food, shelter, breeding and nursery grounds. As such, these vegetated wetland environments along with sandbars, mudflats, rocky foreshores and reefs have significant economic value as well as their intrinsic aesthetic and ecological values. This report summarises the results of the mapping undertaken in the Gulf of Carpentaria Region from the Queensland/Northern Territory border eastwards to the western bank of the Flinders River (hereafter called the Gulf Study Area). The study was undertaken in order to: 1. document and map coastal wetlands of the Gulf Study Area; 2. document levels of existing disturbance to and protection of these wetlands; 3. examine existing recreational, indigenous and commercial fisheries of the region; 4. evaluate the conservation values of the areas investigated from the viewpoint of fisheries productivity and as habitat for important and/or threatened species for future FHA/Marine Protected Area (MPA) declaration. Dataset URL Link: Queensland Coastal Wetlands Resources Mapping data. [Dataset]

Queensland Coastal Wetland Resources: Sand Bay to Keppel Bay.

Protection of coastal wetland environments is an important prerequisite to effective and sustainable inshore fisheries management and conservation of habitats for use by future generations. Mangroves, saltmarshes, seagrasses and non vegetated habitats directly support local and regional inshore and offshore fisheries through the provision of food, shelter, breeding and nursery grounds. As such, these wetland environments have significant economic value as well as their intrinsic aesthetic and ecological values. This report summarises the results of the mapping undertaken in the Central Queensland Coast from Sand Bay to Keppel Bay (hereafter referred to as the Study Area). The study was undertaken in order to: 1. document and map the coastal wetland communities along the Queensland coastline from Sand Bay (20.93°S, 149.04°E) to Keppel Bay (23.65°S, 151.07°E); 2. document levels of existing disturbance to and protection of the wetlands; 3. examine existing recreational and commercial fisheries in the region; and 4. evaluate the conservation values of the areas investigated from the viewpoint of fisheries productivity and as habitat for important and/or threatened species. Dataset URL Link: Queensland Coastal Wetlands Resources Mapping data. [Dataset]

Queensland Coastal Wetland Resources: Cape Tribulation to Bowling Green Bay

This report provides key resource data for the ongoing assessment of the requirement for additional Marine Protected Areas (e.g. FHAs under the Queensland Fisheries Act 1994) in regions of high fish habitat value in northern Queensland from Cape Tribulation to Bowling Green Bay (hereafter referred to as the Study Area). The study also provides baseline information on the coastal wetlands within this Study Area for consideration in the Ramsar site nomination process. The Study Area extends from Cape Tribulation (16o 6’S, 145o 24’E) to Bowling Green Bay (19o 30’S, 147o 24’E) in tropical north Queensland. The project aimed to: 1. document and map the coastal wetland communities of the Study Area; 2. document levels of existing disturbance to and protection of the wetlands; 3. examine existing recreational, indigenous and commercial fisheries resources in the region; 4. evaluate the conservation values of the areas investigated from the viewpoint of fisheries productivity and as habitat for important and/or threatened species for future FHA/MPA declaration. Dataset URL Link: Queensland Coastal Wetlands Resources Mapping data. [Dataset]

Coastal Wetlands Resources Investigation of the Burdekin Delta for declaration as fisheries reserves. Report to Ocean Rescue 2000

A project to investigate the coastal wetland resources of the Burdekin Delta, north Queensland, was undertaken as part of the long-term assessment of the coastal fisheries resources of Queensland. Extending from November 1993 to May 1995, fieldwork was undertaken in November 1993 and August 1994. The scope of the coastal wetlands resources investigation of the Burdekin Delta for declaration as a Fish Habitat Area was: 1. To document and map the marine wetland vegetation communities in the Burdekin River delta. 2. To document levels of existing disturbance to wetlands, existing recreational and commercial fisheries resources, and existing fishing activities. 3. To evaluate the conservation values of the areas investigated from the viewpoint of fisheries productivity and as habitat for important/threatened species. 4. To initiate Fish Habitat Area declaration under Section 120 of the Queensland Fisheries Act 1994 with formal consultation to all stakeholders. This report concentrates on Points 1 and 3, the documentation of the marine wetland vegetation communities and the evaluation of conservation values from a fisheries viewpoint. Dataset URL Link: Queensland Coastal Wetlands Resources Mapping data. [Dataset]

Queensland Coastal Wetland Resource Investigation of the Bowen Region: Cape Upstart to Gloucester Island

The wetland resources of the Queensland coastline have been mapped as a baseline dataset for Marine Protected Area investigation and particularly Fish Habitat Area (FHA) declaration, Ramsar site nomination and continued monitoring of these important fish habitats. This report summarises the results of the mapping undertaken in the Bowen region from the East Coast of Cape Upstart (Abbot Bay) to Gloucester Island (encompassing Edgecumbe Bay). The study was undertaken in order to: 1. document and map the coastal wetland communities within the Bowen region; 2. document levels of existing disturbance to and protection of the wetlands; 3. examine existing recreational and commercial fisheries in the region; and 4. evaluate the significance of the coastal wetlands in the region. Dataset URL Link: Queensland Coastal Wetlands Resources Mapping data. [Dataset]

Efficacy of exclusion fencing to protect ephemeral floodplain lagoon habitats from feral pigs (Sus scrofa)

Foraging by feral pigs can strongly affect wetland vegetation assemblages and so too wider ecological processes, although their effects on freshwater ecosystems have seldom been tudied. We assessed the ecological effects of pig foraging in replicate fenced and unfenced ephemeral floodplain lagoons in tropical north-eastern Australia. Pig foraging activities in unfenced lagoons caused major changes to aquatic macrophyte communities and as a consequence, to the proportional amounts of open water and bare ground. The destruction of macrophyte communities and upheaval of wetland sediments significantly affected wetland turbidity, and caused prolonged anoxia and pH imbalances in the unfenced treatments. Whilst fencing of floodplain lagoons will protect against feral pig foraging activities, our repeated measures of many biological, physical and chemical parameters inferred that natural seasonal (i.e. temporal) effects had a greater influence on these variables than did pigs. To validate this observation requires measuring how these effects are influenced by the seemingly greater annual disturbance regime of variable flooding and drying in this tropical climate.

Power system stability implications from electromechanical wave propagation

Electromechanical wave propagation characterizes the first-swing dynamic response in a spatially delayed manner. This paper investigates the characteristics of this phenomenon in two-dimensional and one-dimensional power systems. In 2-D systems, the wave front expands as a ripple in a pond. In 1-D systems, the wave front is more concentrated, retains most of its magnitude, and travels like a pulse on a string. This large wave front is more impactful upon any weak link and easily causes transient instability in 1-D systems. The initial disturbance injects both high and low frequency components, but the lumped nature of realistic systems only permits the lower frequency components to propagate through. The kinetic energy split at a junction is equal to the generator inertia ratio in each branch in an idealized continuum system. This prediction is approximately valid in a realistic power system. These insights can enhance understanding and control of the traveling waves.

On the origin of the inflectional instability of a laminar separation bubble

This is an experimental and theoretical Study of a laminar separation bubble and the associated linear stability mechanisms. Experiments were performed over a flat plate kept in a wind tunnel, with an imposed pressure gradient typical of an aerofoil that would involve a laminar separation bubble. The separation bubble was characterized by measurement of surface-pressure distribution and streamwise velocity using hot-wire anemometry. Single component hot-wire anemometry was also used for a detailed study of the transition dynamics. It was foundthat the so-called dead-air region in the front portion of the bubble corresponded to a region of small disturbance amplitudes, with the amplitude reaching a maximum value close to the reattachment point. An exponential growth rate of the disturbance was seen in the region upstream of the mean maximum height of the bubble, and this was indicative of a linear instability mechanism at work. An infinitesimal disturbance was impulsively introduced into the boundary layer upstream of separation location, and the wave packet was tracked (in an ensemble-averaged sense) while it was getting advected downstream. The disturbance was found to be convective in nature. Linear stability analyses (both the Orr-Sommerfeld and Rayleigh calculations) were performed for mean velocity profiles, starting from an attached adverse-pressure-gradient boundary layer all the way up to the front portion of the separation-bubble region (i.e. up to the end of the dead-air region in which linear evolution of the disturbance could be expected). The conclusion from the present work is that the primary instability mechanism in a separation bubble is inflectional in nature, and its origin can be traced back to upstream of the separation location. In other words, the inviscid inflectional instability of the separated shear layer should be logically seen as an extension of the instability of the upstream attached adverse-pressure-gradient boundary layer. This modifies the traditional view that pegs the origin of the instability in a separation bubble to the detached shear layer Outside the bubble, with its associated Kelvin-Helmholtz mechanism. We contendthat only when the separated shear layer has moved considerably away from the wall (and this happens near the maximum-height location of the mean bubble), a description by the Kelvin-Helmholtz instability paradigm, with its associated scaling principles, Could become relevant. We also propose a new scaling for the most amplified frequency for a wall-bounded shear layer in terms of the inflection-point height and the vorticity thickness and show it to be universal.

Thermodynamic properties of Pb2PtO4 and PbPt2O4 and phase equilibria in the system Pb–Pt–O

The compounds Pb2PtO4 and PbPt2O4 were synthesized from an intimate mixture of yellow PbO and Pt metal powders by heating under pure oxygen gas at 973 K for periods up to 600 ks with intermediate grinding and recompacting. Both compounds were found to decompose on heating in pure oxygen to PbO and Pt, apparently in conflict with the requirements for equilibrium phase relations in the ternary system Pb–Pt–O. The oxygen chemical potential corresponding to the three-phase mixtures, Pb2PtO4 + PbO + Pt and PbPt2O4 + PbO + Pt were measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the solid electrolyte and pure oxygen gas at 0.1 MPa pressure as the reference electrode. The standard Gibbs free energies of formation of the ternary oxides were derived from the measurements. Analysis of the results indicated that the equilibrium involving three condensed phases Pb2PtO4 + PbO + Pt is metastable. Under equilibrium conditions, Pb2PtO4 should have decomposed to a mixture of PbO and PbPt2O4. Measurement of the oxygen potential corresponding to this equilibrium decomposition as a function of temperature indicated that decomposition temperature in pure oxygen is 1014(±2) K. This was further confirmed by direct determination of phase relations in the ternary Pb–Pt–O by equilibrating several compositions at 1023 K for periods up to 850 ks and phase identification of quenched samples using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Only one ternary oxide PbPt2O4 was stable at 1023 K under equilibrium conditions. Alloys and intermetallic compounds along the Pb–Pt binary were in equilibrium with PbO.

High temperature stability of oxysulfides containing Ce3+ and Y3+ ions

Standard Gibbs energies of formation of oxysulfides of cerium and yttrium from their respective oxedes were determined using solid oxide galvanic cells incorporating calcia-stabilized zirconia as the electrolyte in the temperature range 870–1120 K. The sulfur potential over the electrode containing the oxide and oxysulfide was fixed by a buffer mixture of Ag + Ag2S. A small amount of CaH2 was added to the buffer to generate an equilibrium ratio of H2S and H2 species in a closed system containing the buffer and the electrode. The sulfur potential is transmitted to the electrode via the gas phase. The results can be summarized by the equations 2left angle bracketCeO2right-pointing angle bracket+1/2(S2)→left angle bracketCe2O2Sright-pointing angle bracket+(O2) ΔG°=430600−109·7T(±400)J mol−1 left angle bracketY2O3right-pointing angle bracket+1/2(S2)→left angle bracketY2O2Sright-pointing angle bracket+1/2(O2) ΔG°=114780−1·45T(±200)J mol−1 The values are compared with data reported in the literature. The stability field diagram for the Ce---O---S system has been developed using the results of this study for Ce2O2S and data for other phases from the literature.

Resilience of a high-conservation-value, semi-arid grassland on fertile clay soils to burning, mowing and ploughing.

In grassland reserves, managed disturbance is often necessary to maintain plant species diversity. We carried out experiments to determine the impact of fire, kangaroo grazing, mowing and disc ploughing on grassland species richness and composition in a nature reserve in semi-arid eastern Australia. Vegetation response was influenced by winter-spring drought after establishment of the experiments, but moderate rainfall followed in late summer-autumn. Species composition varied greatly between sampling times, and the variability due to rainfall differences between seasons and years was greater than the effects of fire, kangaroo grazing, mowing or disc ploughing. In the fire experiment, species richness and composition recovered more rapidly after spring than autumn burning. Species richness and composition were similar to control sites within 12 months of burning and mowing, suggesting that removal of the dominant grass canopy is unnecessary to enhance plant diversity. Two fires (separated by 3 years) and post-fire kangaroo grazing had only minor influence on species richness and composition. Even disc ploughing caused only a small reduction in native richness. The minor impact of ploughing was explained by the small areas that were ploughed, the once-off nature of the treatment, and the high degree of natural movement and cracking in these shrink-swell soils. Recovery of the composition and richness of these grasslands was rapid because of the high proportion of perennial species that resprout vegetatively after fire and mowing. There appears to be little conservation benefit from fire, mowing or ploughing ungrazed areas, as we could identify no native plant species dependent on frequent disturbance for persistence in this grassland community. However, the ability of the Astrebla- and Dichanthium-dominated grasslands to recover quickly after disturbance, given favourable seasonal conditions, suggests that they are well adapted to natural disturbances (e.g. droughts, fire, flooding and native grazing).

Sleep deprivation and brain energy metabolism : in vivo studies in rats and humans

Sleep deprivation leads to increased subsequent sleep length and depth and to deficits in cognitive performance in humans. In animals extreme sleep deprivation is eventually fatal. The cellular and molecular mechanisms causing the symptoms of sleep deprivation are unclear. This thesis was inspired by the hypothesis that during wakefulness brain energy stores would be depleted, and they would be replenished during sleep. The aim of this thesis was to elucidate the energy metabolic processes taking place in the brain during sleep deprivation. Endogenous brain energy metabolite levels were assessed in vivo in rats and in humans in four separate studies (Studies I-IV). In the first part (Study I) the effects of local energy depletion on brain energy metabolism and sleep were studied in rats with the use of in vivo microdialysis combined with high performance liquid chromatography. Energy depletion induced by 2,4-dinitrophenol infusion into the basal forebrain was comparable to the effects of sleep deprivation: both increased extracellular concentrations of adenosine, lactate, and pyruvate, and elevated subsequent sleep. This result supports the hypothesis of a connection between brain energy metabolism and sleep. The second part involved healthy human subjects (Studies II-IV). Study II aimed to assess the feasibility of applying proton magnetic resonance spectroscopy (1H MRS) to study brain lactate levels during cognitive stimulation. Cognitive stimulation induced an increase in lactate levels in the left inferior frontal gyrus, showing that metabolic imaging of neuronal activity related to cognition is possible with 1H MRS. Study III examined the effects of sleep deprivation and aging on the brain lactate response to cognitive stimulation. No physiologic, cognitive stimulation-induced lactate response appeared in the sleep-deprived and in the aging subjects, which can be interpreted as a sign of malfunctioning of brain energy metabolism. This malfunctioning may contribute to the functional impairment of the frontal cortex both during aging and sleep deprivation. Finally (Study IV), 1H MRS major metabolite levels in the occipital cortex were assessed during sleep deprivation and during photic stimulation. N-acetyl-aspartate (NAA/H2O) decreased during sleep deprivation, supporting the hypothesis of sleep deprivation-induced disturbance in brain energy metabolism. Choline containing compounds (Cho/H2O) decreased during sleep deprivation and recovered to alert levels during photic stimulation, pointing towards changes in membrane metabolism, and giving support to earlier observations of altered brain response to stimulation during sleep deprivation. Based on these findings, it can be concluded that sleep deprivation alters brain energy metabolism. However, the effects of sleep deprivation on brain energy metabolism may vary from one brain area to another. Although an effect of sleep deprivation might not in all cases be detectable in the non-stimulated baseline state, a challenge imposed by cognitive or photic stimulation can reveal significant changes. It can be hypothesized that brain energy metabolism during sleep deprivation is more vulnerable than in the alert state. Changes in brain energy metabolism may participate in the homeostatic regulation of sleep and contribute to the deficits in cognitive performance during sleep deprivation.

Studies on the pro-oxidative properties and neurotoxic potential of Angeli's salt-derived nitroxyl (HNO/NO-)

The biological function of nitric oxide and its oxidized forms has received a great deal of attention over the past two decades. However much less attention has been focused on the reduced nitric oxide, nitroxyl (HNO). Unlike NO, HNO is highly reactive species and thus it needs to be generated by using donor compounds under experimental conditions. Currently there is only one donor available, Angeli s salt, which releases HNO in a controlled fashion under pysiological conditions. Prior studies have shown the pro-oxidative and cytotoxic potential of Angeli s salt compared to NO donors. The high reactivity of HNO with cysteine thiols is considered to form the biochemical basis for its unique properties compared to other nitrogen oxides. Such thiol modification cold result in disturbances of vital cellular functions and subsequently to death of disturbance sensitive cells, such as neurons. Therefore modification of proteins and lipids was studied in vitro and the potential neurotoxicity was studied in vivo by local infusion of Angeli s salt into the rat central nervous system. The results show that under aerobic in vitro conditions, HNO can, subsequent to autoxidation, cause irreversible oxidative modification of proteins and lipids. These effects are not however seen in cell culture or following infusion of Angeli s salt directly into the rat central nervous tissue likely due to presence of lower oxygen and higher thiol concentration. However, due to high reactivity with thiols, HNO can cause irreversible inactivation of cysteine modification sensitive enzymes such as cysteine proteases papain in vitro and cathepsin B in cell culture. Furthermore it was shown that infusion of HNO releasing Angeli s salt into the rat central nervous system causes necrotic cell death and motor dysfunction following infusion into the lumbal intrathecal space. In conclusion, the acute neurotoxic potential of Angeli s salt was shown to be relatively low, but still higher compared to NO donors. HNO was shown to affect numerous cellular processes which could result in neurotoxicity if HNO was produced in vivo.