Cavity-enhanced laser spectroscopic studies of vibrational overtones of acetylene

This thesis contains five experimental spectroscopic studies that probe the vibration-rotation energy level structure of acetylene and some of its isotopologues. The emphasis is on the development of laser spectroscopic methods for high-resolution molecular spectroscopy. Three of the experiments use cavity ringdown spectroscopy. One is a standard setup that employs a non-frequency stabilised continuous wave laser as a source. In the other two experiments, the same laser is actively frequency stabilised to the ringdown cavity. This development allows for increased repetition rate of the experimental signal and thus the spectroscopic sensitivity of the method is improved. These setups are applied to the recording of several vibration-rotation overtone bands of both H(12)C(12)CH and H(13)C(13)CH. An intra-cavity laser absorption spectroscopy setup that uses a commercial continuous wave ring laser and a Fourier transform interferometer is presented. The configuration of the laser is found to be sub-optimal for high-sensitivity work but the spectroscopic results are good and show the viability of this type of approach. Several ro-vibrational bands of carbon-13 substituted acetylenes are recorded and analysed. Compared with earlier work, the signal-to-noise ratio of a laser-induced dispersed infrared fluorescence experiment is enhanced by more than one order of magnitude by exploiting the geometric characteristics of the setup. The higher sensitivity of the spectrometer leads to the observation of two new symmetric vibrational states of H(12)C(12)CH. The precision of the spectroscopic parameters of some previously published symmetric states is also improved. An interesting collisional energy transfer process is observed for the excited vibrational states and this phenomenon is explained by a simple step-down model.

Population genetics of Australian white sharks reveals fine-scale spatial structure, transoceanic dispersal events and low effective population sizes

Despite international protection of white sharks Carcharodon carcharias, important conservation parameters such as abundance, population structure and genetic diversity are largely unknown. The tissue of 97 predominately juvenile white sharks sampled from spatially distant eastern and southwestern Australian coastlines was sequenced for the mitochondrial DNA (mtDNA) control region and genotyped with 6 nuclear-encoded microsatellite loci. MtDNA population structure was found between the eastern and southwestern coasts (F-ST = 0.142, p < 0.0001), implying female reproductive philopatry. This concurs with recent satellite and acoustic tracking findings which suggest the sustained presence of discrete east coast nursery areas. Furthermore, population subdivision was found between the same regions with biparentally inherited micro satellite markers (F-ST = 0.009, p < 0.05), suggesting that males may also exhibit some degree of reproductive philopatry; 5 sharks captured along the east coast had mtDNA haplotypes that resembled western Indian Ocean sharks more closely than Australian/New Zealand sharks, suggesting that transoceanic dispersal, or migration resulting in breeding, may occur sporadically. Our most robust estimate of contemporary genetic effective population size was low and close to thresholds at which adaptive potential may be lost. For a variety of reasons, these contemporary estimates were at least 1, possibly 2, orders of magnitude below our historical effective size estimates. Population decline could expose these genetically isolated populations to detrimental genetic effects. Regional Australian white shark conservation management units should be implemented until genetic population structure, size and diversity can be investigated in more detail.

Analysis and prevention of extreme vibration in high speed craft - A research framework

Extreme vibration has been reported for small, high speed craft in the maritime sector, with performance and health threatening effects on boat operators and crew. Musculoskeletal injuries are an enduring problem for high speed craft passengers. Spinal or joint injuries and neurological disorders may occur from repetitive pounding over rough water, continued vibration and single impact events. The risk from whole body vibration (WBV) induced through the small vessels mainly depends on time spent on the craft, which can’t be changed in a military scenario; as well as the number of shocks and jolts, and their magnitude and frequency. In the European Union for example, physical agents directives require all employers to control exposure to a number of physical agents including noise and vibration. The EC Vibration Directive 2002/44/EC then sets out regulations for the control of health and safety risks from the exposure of workers to hand arm vibration (HAV) and WBV in the workplace. Australia has exposure standards relating to WBV, AS 2670.1-2001 – Evaluation of human exposure to whole body vibration. This standard is identical to the ISO 2631-1:1997, Mechanical vibration and shock – Evaluation of human exposure to whole-body vibration. Currently, none of the jurisdictions in Australia have specific regulations for vibration exposures in workplaces. However vibration is mentioned to varying degrees in their general regulations, codes of practice and guidance material. WBV on high speed craft is normally caused by “continuous 'hammering' from short steep seas or wind against tide conditions. Shock on High Speed Craft is usually caused by random impacts. Military organisations need the knowledge to make informed decisions regarding their marine operations, compliance with legislation and potentially harmful health effects, and develop and implement appropriate counter-measures. Marine case studies in the UK such as published MAIB (Marine Accident Investigation Branch) reports show injuries that have occurred in operation, and subsequent MCA (Maritime Coastguard Agency) guidance is provided (MGN 436 (M+F), WHOLE-BODY VIBRATION: Guidance on Mitigating Against the Effects of Shocks and Impacts on Small Vessels. MCA, 2011). This paper proposes a research framework to study the origin, impact and pathways for prevention of WBV in small, high speed craft in a maritime environment.

The relationship between forward head posture and cervical muscle performance in healthy individuals

Background Forward head postures (FHP) are proposed to adversely load cervical spine structures. Neck muscles provide support for the neck, and thus an imbalance in neck muscle performance could potentially contribute to the development of FHP. Previous studies have not considered the interaction of multiple muscle groups with regard to postural orientation. Given the interdependence of muscles along the cervical spine for optimal orientation and physical support of the vertebral column, the performance of a single muscle group may not accurately reflect the coordinated ability of the muscles to maintain a neutral neck posture. Purpose The purpose of this study was to investigate the relationship between FHP and the balance between the cervical extensor and flexor muscle groups in healthy individuals. We hypothesised that the magnitude of FHP would be associated with the strength and endurance performance ratios between the cervical extensor and flexor muscle groups. Methods Twenty male and 24 female volunteers were photographed in the sagittal plane wearing surface markers. The FHP of each participant was measured via the tragus-sternum marker distance over two conditions: (1)in relaxed standing and (2)during a sustained sitting task. Maximal strength (Nm) and endurance (s) performance of the extensor and flexor muscle groups were recorded at the upper (craniocervical flexion/extension (CCF/CCE)) and lower (cervicothoracic flexion/extension (CTF/CTE)) cervical regions. Muscle performance measures were expressed as extension:flexion ratios and their relation to FHP evaluated. A stepwise multiple regression analysis using backward elimination was utilised to examine the relationship between the postural measures and the muscle performance ratio measures. Separate models were used for the two different postural conditions (standing, sustained sitting). Gender was included as a constant correction factor in all regression models. Where gender was a significant variable in the model, analyses were repeated separately for males and females. Results Greater FHP in standing was significantly associated with reduced proportional CTE to CCF strength in females (R2 = 0.21, P = 0.03) and greater proportional CTE to CTF strength in males (R2 = 0.23, P = 0.03). A greater drift into FHP during sustained sitting was associated with a relative reduction in CCE endurance proportional to CTF endurance in females only (R2 = 0.27, P = 0.017). Conclusion(s) This initial study indicates that the balance in performance between the cervical flexor and extensor muscle groups may impact FHP in healthy individuals. However, the findings were inconsistent across different muscle performance ratios and gender. Larger scale studies are therefore now needed to further clarify the relationship between FHP and muscle performance. Implications The findings suggest that relative performance of the various cervical muscle groups needs to be accounted for when considering postural correction strategies in the clinical setting, as is often recommended.

Born leaders: Political selection and the relative age effect in the US Congress

We present substantial evidence for the existence of a bias in the distribution of births of leading US politicians in favour of those who were the eldest in their cohort at school. This result adds to the research on the long-term effects of relative age among peers at school. We discuss parametric and non-parametric tests to identify this effect, and we show that it is not driven by measurement error, redshirting or a sorting effect of highly educated parents. The magnitude of the effect that we estimate is larger than what other studies on ‘relative age effects’ have found for broader populations but is in general consistent with research that looks at professional sportsmen. We also find that relative age does not seem to correlate with the quality of elected politicians.

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.

Integration of natural hazards, risk and climate change into spatial planning practices

Most countries of Europe, as well as many countries in other parts of the world, are experiencing an increased impact of natural hazards. It is often speculated, but not yet proven, that climate change might influence the frequency and magnitude of certain hydro-meteorological natural hazards. What has certainly been observed is a sharp increase in financial losses caused by natural hazards worldwide. Eventhough Europe appears to be a space that is not affected by natural hazards to such catastrophic extents as other parts of the world are, the damages experienced here are certainly increasing too. Natural hazards, climate change and, in particular, risks have therefore recently been put high on the political agenda of the EU. In the search for appropriate instruments for mitigating impacts of natural hazards and climate change, as well as risks, the integration of these factors into spatial planning practices is constantly receiving higher attention. The focus of most approaches lies on single hazards and climate change mitigation strategies. The current paradigm shift of climate change mitigation to adaptation is used as a basis to draw conclusions and recommendations on what concepts could be further incorporated into spatial planning practices. Especially multi-hazard approaches are discussed as an important approach that should be developed further. One focal point is the definition and applicability of the terms natural hazard, vulnerability and risk in spatial planning practices. Especially vulnerability and risk concepts are so many-fold and complicated that their application in spatial planning has to be analysed most carefully. The PhD thesis is based on six published articles that describe the results of European research projects, which have elaborated strategies and tools for integrated communication and assessment practices on natural hazards and climate change impacts. The papers describe approaches on local, regional and European level, both from theoretical and practical perspectives. Based on these, passed, current and future potential spatial planning applications are reviewed and discussed. In conclusion it is recommended to shift from single hazard assessments to multi-hazard approaches, integrating potential climate change impacts. Vulnerability concepts should play a stronger role than present, and adaptation to natural hazards and climate change should be more emphasized in relation to mitigation. It is outlined that the integration of risk concepts in planning is rather complicated and would need very careful assessment to ensure applicability. Future spatial planning practices should also consider to be more interdisciplinary, i.e. to integrate as many stakeholders and experts as possible to ensure the sustainability of investments.

Legume pastures can reduce N2O emissions intensity in subtropical cereal cropping systems

Alternative sources of N are required to bolster subtropical cereal production without increasing N2O emissions from these agro-ecosystems. The reintroduction of legumes in cereal cropping systems is a possible strategy to reduce synthetic N inputs but elevated N2O losses have sometimes been observed after the incorporation of legume residues. However, the magnitude of these losses is highly dependent on local conditions and very little data are available for subtropical regions. The aim of this study was to assess whether, under subtropical conditions, the N mineralised from legume residues can substantially decrease the synthetic N input required by the subsequent cereal crop and reduce overall N2O emissions during the cereal cropping phase. Using a fully automated measuring system, N2O emissions were monitored in a cereal crop (sorghum) following a legume pasture and compared to the same crop in rotation with a grass pasture. Each crop rotation included a nil and a fertilised treatment to assess the N availability of the residues. The incorporation of legumes provided enough readily available N to effectively support crop development but the low labile C left by these residues is likely to have limited denitrification and therefore N2O emissions. As a result, N2O emissions intensities (kgN2O-N yield-1ha-1) were considerably lower in the legume histories than in the grass. Overall, these findings indicate that the C supplied by the crop residue can be more important than the soil NO3 - content in stimulating denitrification and that introducing a legume pasture in a subtropical cereal cropping system is a sustainable practice from both environmental and agronomic perspectives.

Growth and physical properties of a new chiral open-framework crystal for NLO applications: Cesium hydrogen l-malate monohydrate

Cesium hydrogen l-malate monohydrate, CsH(C4H4O5)·H2O, is a new chiral open-framework semi-organic crystalline material with a second-harmonic generation efficiency one order of magnitude greater than KDP. Single crystals of this new material have been grown by the conventional slow cooling technique from aqueous solution. Grown crystals display both platy and prismatic morphologies depending on the imposed supersaturation. Hardness values measured using Vickers hardness indenter show considerable anisotropy. The resistivity behavior at room temperature and above, places the crystal between an ionic conductor and a dielectric. The single-crystal SHG efficiency estimated through Maker fringes experiment gives deff which is 4.24 times that of KDP. Single and multiple shot experiments performed on the grown crystals for the fundamental and second harmonic of pulsed Nd:YAG laser (1064 and 532 nm) show that it exhibits a high laser damage threshold which is a favorable property for nonlinear optical applications.

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.

The Occurrence and Toxicity of Indospicine to Grazing Animals

Indospicine is a non-proteinogenic amino acid which occurs in Indigofera species with widespread prevalence in grazing pastures across tropical Africa, Asia, Australia, and the Americas. It accumulates in the tissues of grazing livestock after ingestion of Indigofera. It is a competitive inhibitor of arginase and causes both liver degeneration and abortion. Indospicine hepatoxicity occurs universally across animal species but the degree varies considerably between species, with dogs being particularly sensitive. The magnitude of canine sensitivity is such that ingestion of naturally indospicine-contaminated horse and camel meat has caused secondary poisoning of dogs, raising significant industry concern. Indospicine impacts on the health and production of grazing animals per se has been less widely documented. Livestock grazing Indigofera have a chronic and cumulative exposure to this toxin, with such exposure experimentally shown to induce both hepatotoxicity and embryo-lethal effects in cattle and sheep. In extensive pasture systems, where animals are not closely monitored, the resultant toxicosis may well occur after prolonged exposure but either be undetected, or even if detected not be attributable to a particular cause. Indospicine should be considered as a possible cause of animal poor performance, particularly reduced weight gain or reproductive losses, in pastures where Indigofera are prevalent.

Ultralow noise field-effect transistor from multilayer graphene

We present low-frequency electrical resistance fluctuations, or noise, in graphene-based field-effect devices with varying number of layers. In single-layer devices, the noise magnitude decreases with increasing carrier density, which behaved oppositely in the devices with two or larger number of layers accompanied by a suppression in noise magnitude by more than two orders in the latter case. This behavior can be explained from the influence of external electric field on graphene band structure, and provides a simple transport-based route to isolate single-layer graphene devices from those with multiple layers. ©2009 American Institute of Physics

Isotope shifts and hyperfine structure in the 555.8-nm S-1(0) -> P-3(1) line of Yb

We apply our technique of using a Rb-stabilized ring-cavity resonator to measure the frequencies of various spectral components in the 555.8-nm 1S0-->3P1 line of Yb. We determine the isotope shifts with 60 kHz precision, which is an order-of-magnitude improvement over the best previous measurement on this line. There are two overlapping transitions, 171Yb(1/2-->3/2) and 173Yb(5/2-->3/2), which we resolve by applying a magnetic field. We thus obtain the hyperfine constants in the 3P1 state of the odd isotopes with a significantly improved precision. Knowledge of isotope shifts and hyperfine structure should prove useful for high-precision calculations in Yb necessary to interpret ongoing experiments testing parity and time-reversal symmetry violation in the laws of physics.

Regulation of Testosterone Rhythmicity by Gonadotropins in Bonnet Monkeys (Macaca radiata)

In an attempt to study the factor(s) that regulates production of nychthemeral testosterone surges in adult male bonnet monkeys (Macaca radiata), serum levels of testosterone, LH, FSH, and prolactin were monitored during a 24 h period. Only prolactin showed a significant increment in its levels coincident with that of the testosterone surge. The relationship between LH and testosterone production was studied by 1) observing the responsiveness of testes, in terms of testosterone production, to one or two injections of oLH (1 mg/injection) given 12 h apart at 0900 and 2100 h; and 2) monitoring the effect on testicular testosterone production of LH antiserum injection given at 1000, 1700, and 2100 h. That each LH injection brought about an increment in testosterone level of equal magnitude suggests that the difference in responsiveness of the testes to unchanging levels of LH at morning and night hours is not due to any alteration in substrate availability at the two time intervals. The LH antiserum experiments indicate that irrespective of the time of its administration the nocturnal surge of testosterone, which normally occurs at 2200 h, is blocked. While the antiserum prevents a rise in testosterone level, it appears not to influence basal testosterone production. The results further show that even at 2100 h, when surge testosterone production is already initiated, the testis is still highly sensitive to lack of LH, antiserum injection bringing about within 2 h a significant reduction in testosterone levels (by 69% in experimentals vs 11% in controls).

Fine-tuning of unmanned aerial surveillance for ecological systems

Much of our understanding and management of ecological processes requires knowledge of the distribution and abundance of species. Reliable abundance or density estimates are essential for managing both threatened and invasive populations, yet are often challenging to obtain. Recent and emerging technological advances, particularly in unmanned aerial vehicles (UAVs), provide exciting opportunities to overcome these challenges in ecological surveillance. UAVs can provide automated, cost-effective surveillance and offer repeat surveys for pest incursions at an invasion front. They can capitalise on manoeuvrability and advanced imagery options to detect species that are cryptic due to behaviour, life-history or inaccessible habitat. UAVs may also cause less disturbance, in magnitude and duration, for sensitive fauna than other survey methods such as transect counting by humans or sniffer dogs. The surveillance approach depends upon the particular ecological context and the objective. For example, animal, plant and microbial target species differ in their movement, spread and observability. Lag-times may exist between a pest species presence at a site and its detectability, prompting a need for repeat surveys. Operationally, however, the frequency and coverage of UAV surveys may be limited by financial and other constraints, leading to errors in estimating species occurrence or density. We use simulation modelling to investigate how movement ecology should influence fine-scale decisions regarding ecological surveillance using UAVs. Movement and dispersal parameter choices allow contrasts between locally mobile but slow-dispersing populations, and species that are locally more static but invasive at the landscape scale. We find that low and slow UAV flights may offer the best monitoring strategy to predict local population densities in transects, but that the consequent reduction in overall area sampled may sacrifice the ability to reliably predict regional population density. Alternative flight plans may perform better, but this is also dependent on movement ecology and the magnitude of relative detection errors for different flight choices. Simulated investigations such as this will become increasingly useful to reveal how spatio-temporal extent and resolution of UAV monitoring should be adjusted to reduce observation errors and thus provide better population estimates, maximising the efficacy and efficiency of unmanned aerial surveys.