Novel Organo-Noble-Gas Hydrides

Noble gases are mostly known as inert monatomic gases due to their limited reactivity with other elements. However, the first predictions of noble-gas compounds were suggested by Kossel in 1916, by von Antropoff in 1924, and by Pauling in 1930. It took many decades until the first noble-gas compound, XePtF6, was synthesized by Neil Bartlett in 1962. This was followed by gradual development of the field and many noble-gas compounds have been prepared. In 1995, a family of noble-gas hydride molecules was discovered at the University of Helsinki. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. The first molecular species made include HXeI, HXeBr, HXeCl, HKrCl and HXeH. Nowadays the total number of prepared HNgY molecules is 23 including both inorganic and organic compounds. The first and only neutral ground-state argon compound, HArF, was synthetized in 2000. Helium and neon are the only elements in the periodic table that do not form neutral, ground-state molecules. In this Thesis, experimental preparation of eight novel xenon- and krypton-containing organo-noble-gas hydrides made from acetylene (HCCH), diacetylene (HCCCCH) and cyanoacetylene (HCCCN) are presented. These novel species include the first organic krypton compound, HKrCCH, as well as the first noble-gas hydride molecule containing two Xe atoms, HXeCCXeH. Other new compounds are HXeCCH, HXeCC, HXeC4H, HKrC4H, HXeC3N, and HKrC3N. These molecules are prepared in noble-gas matrices (krypton or xenon) using ultraviolet photolysis of the precursor molecule and thermal mobilization of the photogenerated H atoms. The molecules were identified using infrared spectroscopy and ab initio calculations. The formation mechanisms of the organo-noble-gas molecules are studied and discussed in this context. The focus is to evidence experimentally the neutral formation mechanisms of HNgY molecules upon global mobility of H atoms. The formation of HXeCCXeH from another noble-gas compound (HXeCC) is demonstrated and discussed. Interactions with the surrounding matrix and molecular complexes of the HXeCCH molecule are studied. HXeCCH was prepared in argon and krypton solids in addition to a Xe matrix. The weak HXeCCH∙∙∙CO2 complex is prepared and identified. Preparation of the HXeCCH∙∙∙CO2 complex demonstrates an advanced approach to studies of HNgY complexes where the precursor complex (HCCH∙∙∙CO2) is obtained using photolysis of a larger molecule (propiolic acid).

Does lethal control of top-predators release mesopredators? A re-evaluation of three Australian case studies

Top-predators can sometimes be important for structuring fauna assemblages in terrestrial ecosystems. Through a complex trophic cascade, the lethal control of top-predators has been predicted to elicit positive population responses from mesopredators that may in turn increase predation pressure on prey species of concern. In support of this hypothesis, many relevant research papers, opinion pieces and literature reviews identify three particular case studies as supporting evidence for top-predator control-induced release of mesopredators in Australia. However, many fundamental details essential for supporting this hypothesis are missing from these case studies, which were each designed to investigate alternative aims. Here, we re-evaluate the strength of evidence for top-predator control-induced mesopredator release from these three studies after comprehensive analyses of associated unpublished correlative and experimental data. Circumstantial evidence alluded to mesopredator releases of either the European Red Fox (Vulpes vulpes) or feral Cat (Felis catus) coinciding with Dingo (Canis lupus dingo) control in each case. Importantly, however, substantial limitations in predator population sampling techniques and/or experimental designs preclude strong assertions about the effect of lethal control on mesopredator populations from these studies. In all cases, multiple confounding factors and plausible alternative explanations for observed changes in predator populations exist. In accord with several critical reviews and a growing body of demonstrated experimental evidence on the subject, we conclude that there is an absence of reliable evidence for top-predator control-induced mesopredator release from these three case studies. Well-designed and executed studies are critical for investigating potential top-predator control-induced mesopredator release.

Resting pastures to improve land condition in northern Australia: guidelines based on the literature and simulation modelling

Pasture rest is a possible strategy for improving land condition in the extensive grazing lands of northern Australia. If pastures currently in poor condition could be improved, then overall animal productivity and the sustainability of grazing could be increased. The scientific literature is examined to assess the strength of the experimental information to support and guide the use of pasture rest, and simulation modelling is undertaken to extend this information to a broader range of resting practices, growing conditions and initial pasture condition. From this, guidelines are developed that can be applied in the management of northern Australia’s grazing lands and also serve as hypotheses for further field experiments. The literature on pasture rest is diverse but there is a paucity of data from much of northern Australia as most experiments have been conducted in southern and central parts of Queensland. Despite this, the limited experimental information and the results from modelling were used to formulate the following guidelines. Rest during the growing season gives the most rapid improvement in the proportion of perennial grasses in pastures; rest during the dormant winter period is ineffective in increasing perennial grasses in a pasture but may have other benefits. Appropriate stocking rates are essential to gain the greatest benefit from rest: if stocking rates are too high, then pasture rest will not lead to improvement; if stocking rates are low, pastures will tend to improve without rest. The lower the initial percentage of perennial grasses, the more frequent the rests should be to give a major improvement within a reasonable management timeframe. Conditions during the growing season also have an impact on responses with the greatest improvement likely to be in years of good growing conditions. The duration and frequency of rest periods can be combined into a single value expressed as the proportion of time during which resting occurs; when this is done the modelling suggests the greater the proportion of time that a pasture is rested, the greater is the improvement but this needs to be tested experimentally. These guidelines should assist land managers to use pasture resting but the challenge remains to integrate pasture rest with other pasture and animal management practices at the whole-property scale.

Modelling the manager: Representing rule-based management in farming systems simulation models

We trace the evolution of the representation of management in cropping and grazing systems models, from fixed annual schedules of identical actions in single paddocks toward flexible scripts of rules. Attempts to define higher-level organizing concepts in management policies, and to analyse them to identify optimal plans, have focussed on questions relating to grazing management owing to its inherent complexity. “Rule templates” assist the re-use of complex management scripts by bundling commonly-used collections of rules with an interface through which key parameters can be input by a simulation builder. Standard issues relating to parameter estimation and uncertainty apply to management sub-models and need to be addressed. Techniques for embodying farmers' expectations and plans for the future within modelling analyses need to be further developed, especially better linking planning- and rule-based approaches to farm management and analysing the ways that managers can learn.

Quantifying the response of cotton production in eastern Australia to climate change

Abstract The paper evaluates the effect of future climate change (as per the CSIRO Mk3.5 A1FI future climate projection) on cotton yield in Southern Queensland and Northern NSW, eastern Australia by using of the biophysical simulation model APSIM (Agricultural Production Systems sIMulator). The simulations of cotton production show that changes in the influential meteorological parameters caused by climate change would lead to decreased future cotton yields without the effect of CO2 fertilisation. By 2050 the yields would decrease by 17 %. Including the effects of CO2 fertilisation ameliorates the effect of decreased water availability and yields increase by 5.9 % by 2030, but then decrease by 3.6 % in 2050. Importantly, it was necessary to increase irrigation amounts by almost 50 % to maintain adequate soil moisture levels. The effect of CO2 was found to have an important positive impact of the yield in spite of deleterious climate change. This implies that the physiological response of plants to climate change needs to be thoroughly understood to avoid making erroneous projections of yield and potentially stifling investment or increasing risk.

Intermolecular Interactions of Noble-Gas-Containing Species

The importance of intermolecular interactions to chemistry, physics, and biology is difficult to overestimate. Without intermolecular forces, condensed phase matter could not form. The simplest way to categorize different types of intermolecular interactions is to describe them using van der Waals and hydrogen bonded (H-bonded) interactions. In the H-bond, the intermolecular interaction appears between a positively charged hydrogen atom and electronegative fragments and it originates from strong electrostatic interactions. H-bonding is important when considering the properties of condensed phase water and in many biological systems including the structure of DNA and proteins. Vibrational spectroscopy is a useful tool for studying complexes and the solvation of molecules. Vibrational frequency shift has been used to characterize complex formation. In an H-bonded system A∙∙∙H-X (A and X are acceptor and donor species, respectively), the vibrational frequency of the H-X stretching vibration usually decreases from its value in free H-X (red-shift). This frequency shift has been used as evidence for H-bond formation and the magnitude of the shift has been used as an indicator of the H-bonding strength. In contrast to this normal behavior are the blue-shifting H-bonds, in which the H-X vibrational frequency increases upon complex formation. In the last decade, there has been active discussion regarding these blue-shifting H-bonds. Noble-gases have been considered inert due to their limited reactivity with other elements. In the early 1930 s, Pauling predicted the stable noble-gas compounds XeF6 and KrF6. It was not until three decades later Neil Bartlett synthesized the first noble-gas compound, XePtF6, in 1962. A renaissance of noble-gas chemistry began in 1995 with the discovery of noble-gas hydride molecules at the University of Helsinki. The first hydrides were HXeCl, HXeBr, HXeI, HKrCl, and HXeH. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. At present, this class of molecules comprises 23 members including both inorganic and organic compounds. The first and only argon-containing neutral chemical compound HArF was synthesized in 2000 and its properties have since been investigated in a number of studies. A helium-containing chemical compound, HHeF, was predicted computationally, but its lifetime has been predicted to be severely limited by hydrogen tunneling. Helium and neon are the only elements in the periodic table that do not form neutral, ground state molecules. A noble-gas matrix is a useful medium in which to study unstable and reactive species including ions. A solvated proton forms a centrosymmetric NgHNg+ (Ng = Ar, Kr, and Xe) structure in a noble-gas matrix and this is probably the simplest example of a solvated proton. Interestingly, the hypothetical NeHNe+ cation is isoelectronic with the water-solvated proton H5O2+ (Zundel-ion). In addition to the NgHNg+ cations, the isoelectronic YHY- (Y = halogen atom or pseudohalogen fragment) anions have been studied with the matrix-isolation technique. These species have been known to exist in alkali metal salts (YHY)-M+ (M = alkali metal e.g. K or Na) for more than 80 years. Hydrated HF forms the FHF- structure in aqueous solutions, and these ions participate in several important chemical processes. In this thesis, studies of the intermolecular interactions of HNgY molecules and centrosymmetric ions with various species are presented. The HNgY complexes show unusual spectral features, e.g. large blue-shifts of the H-Ng stretching vibration upon complexation. It is suggested that the blue-shift is a normal effect for these molecules, and that originates from the enhanced (HNg)+Y- ion-pair character upon complexation. It is also found that the HNgY molecules are energetically stabilized in the complexed form, and this effect is computationally demonstrated for the HHeF molecule. The NgHNg+ and YHY- ions also show blue-shifts in their asymmetric stretching vibration upon complexation with nitrogen. Additionally, the matrix site structure and hindered rotation (libration) of the HNgY molecules were studied. The librational motion is a much-discussed solid state phenomenon, and the HNgY molecules embedded in noble-gas matrices are good model systems to study this effect. The formation mechanisms of the HNgY molecules and the decay mechanism of NgHNg+ cations are discussed. A new electron tunneling model for the decay of NgHNg+ absorptions in noble-gas matrices is proposed. Studies of the NgHNg+∙∙∙N2 complexes support this electron tunneling mechanism.

Lucy Dawidowicz papers, 1938-1990.

Contains research notes on American history, some of which were used in her book, _On Equal Terms_. Also contains notes on Antisemitism in America, Holocaust denial, and European Jewish heritage and the Holocaust. Materials also include biographical materials consisting of letters, notes, memorabilia, and photographs. There is also a series of publications: published articles, books, and other materials, along with business correspondence dealing with book publishers and editors. Photographs include those taken during her year in Vilna (1938) until her death in 1990. Correspondence covers the years 1961-1990 and contains letters with many historians, professors, and scholars in the field of Jewish affairs. Also contains personal correspondence with colleagues and friends such as Cynthia Ozick and Marie Syrkin.

Integrating different approaches in the definition of biological stocks: A northern Australian multi-jurisdictional fisheries example using grey mackerel, Scomberomorus semifasciatus

A holistic approach to stock structure studies utilises multiple different techniques on the same individuals sampled from selected populations and combines results across spatial and temporal scales to produce a weight of evidence conclusion. It is the most powerful and reliable source of information to use in formulating resource management and monitoring plans. Few examples of the use of a holistic approach in stock structure studies exist, although more recently this is changing. Using such an approach makes integration of results from each technique challenging. An integrated stock definition (ISD) approach for holistic stock structure studies was developed in this study to aid in the appropriate interpretation of stock structure results to guide the determination of fishery management units. The ISD approach is applied herein to a study of the northern Australian endemic grey mackerel, Scomberomorus semifasciatus (Scombridae). Analyses of genetic (mitochondrial DNA and microsatellites), parasite, otolith stable isotope, and growth data are synthesised to determine the stock structure of S. semifasciatus across northern Australia. Integration of the results from all techniques identified at least six S. semifasciatus stocks for management purposes. Further, the use of the ISD approach provided a simple basis for integrating multiple techniques and for their interpretation. The use of this holistic approach was a powerful tool in providing greater certainty about the appropriate management units for S. semifasciatus. Future stock structure studies investigating spatial management questions in the fisheries context should adopt a holistic approach and apply the ISD approach for a more accurate definition of biological stocks to improve fisheries management.

A participatory systems approach to understanding climate adaptation needs

Emerging literature on climate adaptation suggests the need for effective ways of engaging or activating communities and supporting community roles, coupled with whole-of-system approaches to understanding climate change and adaptation needs. We have developed and evaluated a participatory approach to elicit community and stakeholder understanding of climate change adaptation needs, and connect diverse community members and local office bearers towards potential action. The approach was trialed in a series of connected social-ecological systems along a transect from a rural area to the coast and islands of ecologically sensitive Moreton Bay in Queensland, Australia. We conducted ‘climate roundtables’ in each of three areas along the transect, then a fourth roundtable reviewed and extended the results to the region as a whole. Influence diagrams produced through the process show how each climate variable forecast to affect this region (heat, storm, flood, sea-level rise, fire, drought) affects the natural environment, infrastructure, economic and social behaviour patterns, and psychosocial responses, and how sets of people, species and ecosystems are affected, and act, differentially. The participatory process proved effective as a way of building local empathy, a local knowledge base and empowering participants to join towards future climate adaptation action. Key principles are highlighted to assist in adapting the process for use elsewhere.

Integrating pest population models with biophysical crop models to better represent the farming system

Farming systems frameworks such as the Agricultural Production Systems simulator (APSIM) represent fluxes through the soil, plant and atmosphere of the system well, but do not generally consider the biotic constraints that function within the system. We designed a method that allowed population models built in DYMEX to interact with APSIM. The simulator engine component of the DYMEX population-modelling platform was wrapped within an APSIM module allowing it to get and set variable values in other APSIM models running in the simulation. A rust model developed in DYMEX is used to demonstrate how the developing rust population reduces the crop's green leaf area. The success of the linking process is seen in the interaction of the two models and how changes in rust population on the crop's leaves feedback to the APSIM crop modifying the growth and development of the crop's leaf area. This linking of population models to simulate pest populations and biophysical models to simulate crop growth and development increases the complexity of the simulation, but provides a tool to investigate biotic constraints within farming systems and further moves APSIM towards being an agro-ecological framework.

Boosting the productivity and profitability of northern Australian beef enterprises: Exploring innovation options using simulation modelling and systems analysis

The financial health of beef cattle enterprises in northern Australia has declined markedly over the last decade due to an escalation in production and marketing costs and a real decline in beef prices. Historically, gains in animal productivity have offset the effect of declining terms of trade on farm incomes. This raises the question of whether future productivity improvements can remain a key path for lifting enterprise profitability sufficient to ensure that the industry remains economically viable over the longer term. The key objective of this study was to assess the production and financial implications for north Australian beef enterprises of a range of technology interventions (development scenarios), including genetic gain in cattle, nutrient supplementation, and alteration of the feed base through introduced pastures and forage crops, across a variety of natural environments. To achieve this objective a beef systems model was developed that is capable of simulating livestock production at the enterprise level, including reproduction, growth and mortality, based on energy and protein supply from natural C4 pastures that are subject to high inter-annual climate variability. Comparisons between simulation outputs and enterprise performance data in three case study regions suggested that the simulation model (the Northern Australia Beef Systems Analyser) can adequately represent the performance beef cattle enterprises in northern Australia. Testing of a range of development scenarios suggested that the application of individual technologies can substantially lift productivity and profitability, especially where the entire feedbase was altered through legume augmentation. The simultaneous implementation of multiple technologies that provide benefits to different aspects of animal productivity resulted in the greatest increases in cattle productivity and enterprise profitability, with projected weaning rates increasing by 25%, liveweight gain by 40% and net profit by 150% above current baseline levels, although gains of this magnitude might not necessarily be realised in practice. While there were slight increases in total methane output from these development scenarios, the methane emissions per kg of beef produced were reduced by 20% in scenarios with higher productivity gain. Combinations of technologies or innovative practices applied in a systematic and integrated fashion thus offer scope for providing the productivity and profitability gains necessary to maintain viable beef enterprises in northern Australia into the future.

Effective earth and space science analogies

There are several good reasons why Earth and Space Science should be a part of any science curriculum. Nearly everything we do each day is connected in some way to the Earth: to its land, oceans, atmosphere, plants and animals. By 2025, eight billion people will live on Earth. If we are to continue extracting resources to maintain a high quality of life, then it is important that our children are scientifically literate in a way that allows them to exploit the Earth’s resources in a sustainable way. People who understand how earth systems work can make informed decisions and may be able to help resolve issues surrounding clean water, urban planning and development, global climate change and the use and management of natural resources.

Natural convection in rectangular cavities at high Rayleigh number

Natural convection in rectangular two-dimensional cavities with differentially heated side walls is a standard problem in numerical heat transfer. Most of the existing studies has considered the low Ra laminar regime. The general thrust of the present research is to investigate higher Ra flows extending into the unsteady and turbulent regimes where the physics is not fully understood and appropriate models for turbulence are not yet established. In the present study the Boussinesq approximation is being used, but the theoretical background and some preliminary results have been obtained[1] for flows with variable properties.