Controls on iron in soils and soil waters of a forested, coastal catchment in subtropical Australia

Soluble organic matter derived from exotic Pinus vegetation forms stronger complexes with iron (Fe) than the soluble organic matter derived from most native Australian species. This has lead to concern about the environmental impacts related to the establishment of extensive exotic Pinus plantations in coastal southeast Queensland, Australia. It has been suggested that the Pinus plantations may enhance the solubility of Fe in soils by increasing the amount of organically complexed Fe. While this remains inconclusive, the environmental impacts of an increased flux of dissolved, organically complexed Fe from soils to the fluvial system and then to sensitive coastal ecosystems are potentially damaging. Previous work investigated a small number of samples, was largely laboratory based and had limited application to field conditions. These assessments lacked field-based studies, including the comparison of the soil water chemistry of sites associated with Pinus vegetation and undisturbed native vegetation. In addition, the main controls on the distribution and mobilisation of Fe in soils of this subtropical coastal region have not been determined. This information is required in order to better understand the relative significance of any Pinus enhanced solubility of Fe. The main aim of this thesis is to determine the controls on Fe distribution and mobilisation in soils and soil waters of a representative coastal catchment in southeast Queensland (Poona Creek catchment, Fraser Coast) and to test the effect of Pinus vegetation on the solubility and speciation of Fe. The thesis is structured around three individual papers. The first paper identifies the main processes responsible for the distribution and mobilisation of labile Fe in the study area and takes a catchment scale approach. Physicochemical attributes of 120 soil samples distributed throughout the catchment are analysed, and a new multivariate data analysis approach (Kohonen’s self organising maps) is used to identify the conditions associated with high labile Fe. The second paper establishes whether Fe nodules play a major role as an iron source in the catchment, by determining the genetic mechanism responsible for their formation. The nodules are a major pool of Fe in much of the region and previous studies have implied that they may be involved in redox-controlled mobilisation and redistribution of Fe. This is achieved by combining a detailed study of a ferric soil profile (morphology, mineralogy and micromorphology) with the distribution of Fe nodules on a catchment scale. The third component of the thesis tests whether the concentration and speciation of Fe in soil solutions from Pinus plantations differs significantly from native vegetation soil solutions. Microlysimeters are employed to collect unaltered, in situ soil water samples. The redox speciation of Fe is determined spectrophotometrically and the interaction between Fe and dissolved organic matter (DOM) is modelled with the Stockholm Humic Model. The thesis provides a better understanding of the controls on the distribution, concentration and speciation of Fe in the soils and soil waters of southeast Queensland. Reductive dissolution is the main mechanism by which mobilisation of Fe occurs in the study area. Labile Fe concentrations are low overall, particularly in the sandy soils of the coastal plain. However, high labile Fe is common in seasonally waterlogged and clay-rich soils which are exposed to fluctuating redox conditions and in organic-rich soils adjacent to streams. Clay-rich soils are most common in the upper parts of the catchment. Fe nodules were shown to have a negligible role in the redistribution of dissolved iron in the catchment. They are formed by the erosion, colluvial transport and chemical weathering of iron-rich sandstones. The ferric horizons, in which nodules are commonly concentrated, subsequently form through differential biological mixing of the soil. Whereas dissolution/ reprecipitation of the Fe cements is an important component of nodule formation, mobilised Fe reprecipitates locally. Dissolved Fe in the soil waters is almost entirely in the ferrous form. Vegetation type does not affect the concentration and speciation of Fe in soil waters, although Pinus DOM has greater acidic functional group site densities than DOM from native vegetation. Iron concentrations are highest in the high DOM soil waters collected from sandy podosols, where they are controlled by redox potential. Iron concentrations are low in soil solutions from clay and iron oxide rich soils, in spite of similar redox potentials. This is related to stronger sorption to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for microbial metabolisation and reductive dissolution of Fe. Modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxidising conditions. Thus, inputs of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides and increase the flux of dissolved iron out of the catchment. Such inputs are most likely from the lower catchment, where podosols planted with Pinus are most widely distributed. Significant outcomes other than the main aims were also achieved. It is shown that mobilisation of Fe in podosols can occur as dissolved Fe(II) rather than as Fe(III)-organic complexes. This has implications for the large body of work which assumes that Fe(II) plays a minor role. Also, the first paper demonstrates that a data analysis approach based on Kohonen’s self organising maps can facilitate the interpretation of complex datasets and can help identify geochemical processes operating on a catchment scale.

The Attack on Political Correctness: Islamophobia and the Erosion of Multiculturalism In Australia Under the Howard Regime

This article reports on civil society in Australia between 1996 and 2007 related to former Prime Minister John Howard. The article discusses Howard's neo-conservative ideology and Liberal-National coalition, noting his views on political correctness. Howard's administration is also discussed in terms of immigration, multiculturalism, indigenous land rights, othering, and Islamaphobia. Information on the effect of Islamaphobia on Australian perceptions and the treatment of Muslims is also provided

A nation’s role in addressing base erosion and profit shifting : balancing sovereignty with international collaboration and coordination

The notion of sovereignty is central to any international tax issue. While a nation is free to design its tax laws as it sees fit and raise revenue in accordance with the needs of its citizens, it is not possible to undertake such a task in isolation. In a world of cross-border investments and business transactions, all tax regimes impact on one another. Tax interactions between sovereign states cannot be avoided. Ultimately, the interactions mean that a nation must decide whether to engage in both collaboration and coordination with other nations and supranational bodies alike or maintain an individualised stance in relation to its tax policy. Whatever the decision, there is arguably an exercise in national sovereignty in some form. In the context of an international tax regime, whether that regime is interpreted broadly as meaning international norms generally adopted by nations around the world or domestic regimes legislating for cross-border transactions, rhetoric around national fiscal sovereignty takes on many different forms. At one end of the spectrum it is relied upon by financial secrecy jurisdictions (tax havens) as a defence to their position on the basis that ‘other’ nations cannot interfere with the fiscal sovereignty of a jurisdiction. At the other end of the spectrum, it is argued that profit shifting and international tax avoidance if not stopped is, in and of itself, a threat to a nation’s fiscal sovereignty on the basis that it threatens the ability to tax and raise the revenue needed. This paper considers a modern conceptualisation of sovereignty along with its role within international tax coordination and collaboration to argue that a move towards a more unified approach to addressing international base erosion and profit shifting may be the ultimate exercise of national fiscal sovereignty. By using the current transfer pricing regime as a case study, this paper posits that it is not merely enough to have international agreement on allocation rules to be applied, but that the ultimate exercise of national sovereignty is political agreement with other states to ensure that it is governments which determine the allocational basis of worldwide profits to be taxed. In doing so, it is demonstrated that the arm’s length pricing requirement of the current transfer pricing regime, rather than providing governments with the ability to determine the location of profits, is providing multinational entities with the ultimate power to determine that location. If left unchecked, this will eventually erode a nation’s ability to capture the required tax revenue and, as a consequence, may be deemed a failure by nation states to exercise their fiscal sovereignty.

A nation's role in addressing base erosion and profit shifting : sovereignty in relation to transfer pricing

The notion of sovereignty is central to any international tax issue. While a nation is free to design its tax laws as it sees fit and raise revenue in accordance with the needs of its citizens, it is not possible to undertake such a task in isolation. Tax interactions between sovereign states cannot be avoided. Ultimately, the interactions mean that a nation must decide whether or engage in both collaboration and co ordination with other nations and supranational bodies alike or maintain a unilateral stance in relation to its tax policy. This article considers a modern conceptualisation of sovereignty to argue that a move towards a more unified approach to addressing international base erosion and profit sharing may be the ultimate exercise of national fiscal sovereignty.

Matrix metalloproteinase 13-deficient mice are resistant to osteoarthritic cartilage erosion but not chondrocyte hypertrophy or osteophyte development

Objective To investigate the role of matrix metalloproteinase 13 (MMP-13; collagenase 3) in osteoarthritis (OA). Methods OA was surgically induced in the knees of MMP-13-knockout mice and wild-type mice, and mice were compared. Histologic scoring of femoral and tibial cartilage aggrecan loss (0-3 scale), erosion (0-7 scale), and chondrocyte hypertrophy (0-1 scale), as well as osteophyte size (0-3 scale) and maturity (0-3 scale) was performed. Serial sections were stained for type X collagen and the MMP-generated aggrecan neoepitope DIPEN. Results Following surgery, aggrecan loss and cartilage erosion were more severe in the tibia than femur (P < 0.01) and tibial cartilage erosion increased with time (P < 0.05) in wild-type mice. Cartilaginous osteophytes were present at 4 weeks and underwent ossification, with size and maturity increasing by 8 weeks (P < 0.01). There was no difference between genotypes in aggrecan loss or cartilage erosion at 4 weeks. There was less tibial cartilage erosion in knockout mice than in wild-type mice at 8 weeks (P < 0.02). Cartilaginous osteophytes were larger in knockout mice at 4 weeks (P < 0.01), but by 8 weeks osteophyte maturity and size were no different from those in wild-type mice. Articular chondrocyte hypertrophy with positive type X collagen and DIPEN staining occurred in both wild-type and knockout mouse joints. Conclusion Our findings indicate that structural cartilage damage in a mouse model of OA is dependent on MMP-13 activity. Chondrocyte hypertrophy is not regulated by MMP-13 activity in this model and does not in itself lead to cartilage erosion. MMP-13 deficiency can inhibit cartilage erosion in the presence of aggrecan depletion, supporting the potential for therapeutic intervention in established OA with MMP-13 inhibitors.

Superior perilimbal epitheliopathy in recurrent corneal erosion syndrome

Purpose To highlight the finding of occult areas of poor epithelial adhesion in the superior perilimbal cornea in a minority of patients with recalcitrant recurrent corneal erosion syndrome presenting with corneal erosion elsewhere on the corneal surface. Patient population 31 eyes of 31 consecutive patients with corneal erosion undergoing mechanical debridement of the epithelium prior to diamond burr keratectomy for recurrent corneal erosion. Methods Determine the location and incidence of poor epithelial adhesion distant from the initial erosion by use of mechanical debridement with a dry microsponge. Results During debridement, 8 of 31 eyes (25.8%) displayed a large arcuate area of occult dysfunction of adhesion in the superior perilimbal area. None of these patients showed recurrence over a mean of 18 month after diamond burr keratectomy (95% confidence interval 0-36.9%). Conclusion Mechanical debridement with a microsponge identified a significant minority of patients with poor adhesion in the superior perilimbal cornea away from the area of obvious erosion and increased the target area for diamond burr keratectomy. This two pronged approach allowed successful management of this group.

Characterization of alluvial formation by stochastic modelling of paleo-fluvial processes: The concept and method

Modelling fluvial processes is an effective way to reproduce basin evolution and to recreate riverbed morphology. However, due to the complexity of alluvial environments, deterministic modelling of fluvial processes is often impossible. To address the related uncertainties, we derive a stochastic fluvial process model on the basis of the convective Exner equation that uses the statistics (mean and variance) of river velocity as input parameters. These statistics allow for quantifying the uncertainty in riverbed topography, river discharge and position of the river channel. In order to couple the velocity statistics and the fluvial process model, the perturbation method is employed with a non-stationary spectral approach to develop the Exner equation as two separate equations: the first one is the mean equation, which yields the mean sediment thickness, and the second one is the perturbation equation, which yields the variance of sediment thickness. The resulting solutions offer an effective tool to characterize alluvial aquifers resulting from fluvial processes, which allows incorporating the stochasticity of the paleoflow velocity.

Vacuum ultraviolet/atomic oxygen erosion resistance of amorphous Si0.26C0.43N0.31 coating

An amorphous silicon carbonitride (Si1-x-yCxN y, x = 0:43, y = 0:31) coating was deposited on polyimide substrate using the magnetron-sputtering method. Exposure tests of the coated polyimide in atomic oxygen beam and vacuum ultraviolet radiation were performed in a ground-based simulator. Erosion kinetics measurements indicated that the erosion yield of the Si0.26C0.43N0.31 coating was about 1.5x and 1.8 × 10-26 cm3 /atom during exposure in single atomic oxygen beam, simultaneous atomic oxygen beam, and vacuum ultraviolet radiation, respectively. These values were 2 orders of magnitude lower than that of bare polyimide substrate. Scanning electron and atomic force microscopy, X-ray photoelectron spectrometer, and Fourier transformed infrared spectroscopy investigation indicated that during exposures, an oxide-rich layer composed of SiO2 and minor Si-C-O formed on the surface of the Si 0.26C0.43N0.31 coating, which was the main reason for the excellent resistance to the attacks of atomic oxygen. Moreover, vacuum ultraviolet radiation could promote the breakage of chemical bonds with low binding energy, such as C-N, C = N, and C-C, and enhance atomic oxygen erosion rate slightly.

Farm it right : the sustainable farming simulation

Farm It Right is an innovative creative work that simulates sustainable farming techniques using ecological models prepared by academics at Bradford University (School of Life Sciences). This interactive work simulates the farming conditions and options of our ancestors and demonstrates the direct impact their actions had on their environment and on the ’future of their cultures’ (Schmidt 2008). Specifically, the simulation allows users to explore and experiment with the complex relationships between environmental factors and human decision making within the harsh conditions of an early (9th century) Nordic farm. The simulation interface displays both statistical and graphical feedback in response to the users selections regarding animal reproduction rates, shelter provisions, food supplies etc. as well as demonstrating resulting impacts to soil erosion, water supply, animal population sizes etc.---------- 'Farm It Right' is now used at Bradford University (School of Life Sciences) as a dynamic e-Learning resource for incorporating environmental archaeology with sustainable development education, improving the engagement with complex data and the appreciation of human impacts on the environment and the future of their cultures. 'Farm It Right' is also demonstrated as an exemplar case study for interaction design students at Queensland University of Technology.

Evaluation of piezoelectric PVDF polymers for use in space environments. II. Effects of atomic oxygen and vacuum UV exposure

The effects of atomic oxygen (AO) and vacuum UV radiation simulating low Earth orbit conditions on two commercially available piezoelectric polymer films, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE), have been studied. Surface erosion and pattern development are significant for both polymers. Erosion yields were determined as 2.8 � 10�24 cm3/atom for PVDF and 2.5 � 10�24 cm3/atom for P(VDF-TrFE). The piezoelectric properties of the residual material of both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF-TrFE) was observed. A lightly cross-linked network was formed in the copolymer presumably because of penetrating vacuum ultraviolet (VUV) radiation, while the homopolymer remained uncross-linked. These differences were attributed to varying degrees of crystallinity and potentially greater absorption, and hence damage, of VUV radiation in P(VDFTrFE) compared with PVDF.

Effect of simulated space environments on piezoelectric vinylidene flouride-based polymers

Piezoelectric polymers based on polyvinylidene flouride (PVDF) are of interest as adaptive materials for large aperture space-based telescopes. In this study, two piezoelectric polymers, PVDF and P(VDF-TrFE), were exposed to conditions simulating the thermal, radiative and atomic oxygen conditions of low Earth orbit. The degradation pathways were governed by a combination of chemical and physical degradation processes with the molecular changes primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure, as evident from depoling, loss of orientation and surface erosion. The piezoelectric responsiveness of each polymer was strongly dependent on exposure temperature. Radiation and atomic oxygen exposure caused physical and chemical degradation, which would ultimately cause terminal damage of thin films, but did not adversely affect the piezoelectric properties.

Piezoelectric vinylidene-fluoride based polymers for use in space environments

The effects of simulated low earth orbit conditions on vinylidene-fluoride based thin-film piezoelectrics for use in lightweight, large surface area spacecraft such as telescope mirrors and antennae is presented. The environmental factors considered as having the greatest potential to cause damage are temperature, atomic oxygen and vacuum UV radiation. Using the piezoelectric strain coefficients and bimorph deflection measurements the piezoelectric performance over the temperature range -100 to +150°C was studied. The effects of simultaneous AO/VUV exposure were also examined and films characterized by their piezoelectric, surface, and thermal properties. Two fluorinated piezoelectric polymers, poly(vinylidene fluoride) and poly(vinylidene fluoride-co-trifluoroethylene), were adversely affected at elevated temperatures due to depoling caused by randomization of the dipole orientation, while AO/VUV contributed little to depoling but did cause significant surface erosion and, in the case of P(VDF-TrFE), bulk crosslinking. These results highlight the importance of materials selection for use in space environments.

Piezoelectric PVDF materials performance and operation limits in space environments

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films are achieved via charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to suffer due to strong vacuum UV, gamma, X-ray, energetic particles and atomic oxygen under low earth orbit exposure conditions. The degradation of PVDF and its copolymers under various stress environments has been investigated. Initial radiation aging studies using gamma- and e-beam irradiation have shown complex material changes with significant crosslinking, lowered melting and Curie points (where observable), effects on crystallinity, but little influence on overall piezoelectric properties. Surprisingly, complex aging processes have also been observed in elevated temperature environments with annealing phenomena and cyclic stresses resulting in thermal depoling of domains. Overall materials performance appears to be governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and AO exposure is evident as depoling and surface erosion. Major differences between individual copolymers have been observed providing feedback on material selection strategies.