Dynamic axial ligand-site exchange in facially discriminated ruthenium(II) carbonyl and rhodium(III) halide metalloporphyrins

For a series of six-coordinate Ru(II)(CO)L or Rh(III)(X–)L porphyrins which are facially differentiated by having a naphthoquinol- or hydroquinol-containing strap across one face, we show that ligand migration from one face to the other can occur under mild conditions, and that ligand site preference is dependent on the nature of L and X–. For bulky nitrogen-based ligands, the strap can be displaced sideways to accommodate the ligand on the same side as the strap. For the ligand pyrazine, we show 1 H NMR evidence for monodentate and bidentate binding modes on both faces, dependent on ligand concentration and metalloporphyrin structure, and that inter-facial migration is rapid under normal conditions. For monodentate substituted pyridine ligands there is a site dependence on structure, and we show clear evidence of dynamic ligand migration through a series of ligand exchange reactions.

Creating new narratives through shared time and space : the performer/audience connection in multi-site dance events

Site-specific performance provides choices in audience experience via degrees of scale, proximity, levels of immersion and viewing perspectives. Beyond these choices, multi-site promenade events also form a connected audience/performer relationship in which moving together in time and space can produce a shared narrative and aesthetic sensibility of collective, yet individuated and shifting meanings. This paper interrogates this notion through audience/performer experiences in two separate multi-site, dance-led events. here/there/then/now occurred in four intimate sites within the Brisbane Powerhouse, providing a theatricalised platform for audiences to create linked narratives through open-ended and fragmented intertextuality. Accented Body, based on the concept of “the body as site and in site” and notions of connectivity, provided a more expansive platform for a similar, but heightened, shared engagement. Audiences traversed 6 outdoor and 2 indoor Brisbane sites moving to varying levels of a large complex. Eleven, predominantly interactive, screens provided links to other sites as well as to distributed presences in Seoul and London. The differentiation in scale and travel time between sites deepened the immersive experiences of audiences who reported transformative engagements with both site and architecture, accompanied by a sense of extended and yet quickened time.

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.

Iron biogeochemistry and associated greenhouse gas evolution in a forested subtropical Australian coastal catchment : Poona Creek, Southeast Queensland

Iron (Fe) is the fourth most abundant element in the Earth’s crust. Excess Fe mobilization from terrestrial into aquatic systems is of concern for deterioration of water quality via biofouling and nuisance algal blooms in coastal and marine systems. Substantial Fe dissolution and transport involve alternate Fe(II) oxidation followed by Fe(III) reduction, with a diversity of Bacteria and Archaea acting as the key catalyst. Microbially-mediated Fe cycling is of global significance with regard to cycles of carbon (C), sulfur (S) and manganese (Mn). However, knowledge regarding microbial Fe cycling in circumneutral-pH habitats that prevail on Earth has been lacking until recently. In particular, little is known regarding microbial function in Fe cycling and associated Fe mobilization and greenhouse (CO2 and CH4, GHG) evolution in subtropical Australian coastal systems where microbial response to ambient variations such as seasonal flooding and land use changes is of concern. Using the plantation-forested Poona Creek catchment on the Fraser Coast of Southeast Queensland (SEQ), this research aimed to 1) study Fe cycling-associated bacterial populations in diverse terrestrial and aquatic habitats of a representative subtropical coastal circumneutral-pH (4–7) ecosystem; and 2) assess potential impacts of Pinus plantation forestry practices on microbially-mediated Fe mobilization, organic C mineralization and associated GHG evolution in coastal SEQ. A combination of wet-chemical extraction, undisturbed core microcosm, laboratory bacterial cultivation, microscopy and 16S rRNA-based molecular phylogenetic techniques were employed. The study area consisted primarily of loamy sands, with low organic C and dissolved nutrients. Total reactive Fe was abundant and evenly distributed within soil 0–30 cm profiles. Organic complexation primarily controlled Fe bioavailability and forms in well-drained plantation soils and water-logged, native riparian soils, whereas tidal flushing exerted a strong “seawater effect” in estuarine locations and formed a large proportion of inorganic Fe(III) complexes. There was a lack of Fe(II) sources across the catchment terrestrial system. Mature, first-rotation plantation clear-felling and second-rotation replanting significantly decreased organic matter and poorly crystalline Fe in well-drained soils, although variations in labile soil organic C fractions (dissolved organic C, DOC; and microbial biomass C, MBC) were minor. Both well-drained plantation soils and water-logged, native-vegetation soils were inhabited by a variety of cultivable, chemotrophic bacterial populations capable of C, Fe, S and Mn metabolism via lithotrophic or heterotrophic, (micro)aerobic or anaerobic pathways. Neutrophilic Fe(III)-reducing bacteria (FeRB) were most abundant, followed by aerobic, heterotrophic bacteria (heterotrophic plate count, HPC). Despite an abundance of FeRB, cultivable Fe(II)-oxidizing bacteria (FeOB) were absent in associated soils. A lack of links between cultivable Fe, S or Mn bacterial densities and relevant chemical measurements (except for HPC correlated with DOC) was likely due to complex biogeochemical interactions. Neither did variations in cultivable bacterial densities correlate with plantation forestry practices, despite total cultivable bacterial densities being significantly lower in estuarine soils when compared with well-drained plantation soils and water-logged, riparian native-vegetation soils. Given that bacterial Fe(III) reduction is the primary mechanism of Fe oxide dissolution in soils upon saturation, associated Fe mobilization involved several abiotic and biological processes. Abiotic oxidation of dissolved Fe(II) by Mn appeared to control Fe transport and inhibit Fe dissolution from mature, first-rotation plantation soils post-saturation. Such an effect was not observed in clear-felled and replanted soils associated with low SOM and potentially low Mn reactivity. Associated GHG evolution post-saturation mainly involved variable CO2 emissions, with low, but consistently increasing CH4 effluxes in mature, first-rotation plantation soil only. In comparison, water-logged soils in the riparian native-vegetation buffer zone functioned as an important GHG source, with high potentials for Fe mobilization and GHG, particularly CH4 emissions in riparian loam soils associated with high clay and crystalline Fe fractions. Active Fe–C cycling was unlikely to occur in lower-catchment estuarine soils associated with low cultivable bacterial densities and GHG effluxes. As a key component of bacterial Fe cycling, neutrophilic FeOB widely occurred in diverse aquatic, but not terrestrial, habitats of the catchment study area. Stalked and sheathed FeOB resembling Gallionella and Leptothrix were limited to microbial mat material deposited in surface fresh waters associated with a circumneutral-pH seep, and clay-rich soil within riparian buffer zones. Unicellular, Sideroxydans-related FeOB (96% sequence identity) were ubiquitous in surface and subsurface freshwater environments, with highest abundance in estuary-adjacent shallow coastal groundwater water associated with redox transition. The abundance of dissolved C and Fe in the groundwater-dependent system was associated with high numbers of cultivable anaerobic, heterotrophic FeRB, microaerophilic, putatively lithotrophic FeOB and aerobic, heterotrophic bacteria. This research represents the first study of microbial Fe cycling in diverse circumneutral-pH environments (terrestrial–aquatic, freshwater–estuarine, surface–subsurface) of a subtropical coastal ecosystem. It also represents the first study of its kind in the southern hemisphere. This work highlights the significance of bacterial Fe(III) reduction in terrestrial, and bacterial Fe(II) oxidation in aquatic catchment Fe cycling. Results indicate the risk of promotion of Fe mobilization due to plantation clear-felling and replanting, and GHG emissions associated with seasonal water-logging. Additional significant outcomes were also achieved. The first direct evidence for multiple biomineralization patterns of neutrophilic, microaerophilic, unicellular FeOB was presented. A putatively pure culture, which represents the first cultivable neutrophilic FeOB from the southern hemisphere, was obtained as representative FeOB ubiquitous in diverse catchment aquatic habitats.

Big, bigger, best? The impact of reforms on the not-for-profit sector in Queensland

Organisations within the not-for-profit sector provide services to individuals and groups that government and for-profit organisations cannot or will not consider. The not-for-profit sector has come to be a vibrant and rich agglomeration of services and programs that operate under a myriad of philosophical stances, service orientation, client groupings and operational capacities. In Australia these organisations and services are providing social support and service assistance to many people in the community; often targeting their assistance to the most difficult of clients. Initially, in undertaking this role, the not-for-profit sector received limited sponsorship from government. Over time governments assumed greater responsibility in the form of service grants to particular groups: ‘the worthy poor’. More recently, they have entered into contractual service agreements with the not-for-profit sector, which specify the nature of the outcomes to be achieved and, to a degree, the way in which the services will be provided. A consequence of this growing shift to a more marketised model of service contracting, often offered-up under the label of enhanced collaborative practice, has been increased competitiveness between agencies that had previously worked well together (Keast and Brown, 2006). Another trend emerging from the market approach is the entrance of for-profit providers. These larger organisations have higher levels of organisational capacity with considerable organisational slack to allow them to adopt new service roles. Shaped almost as ‘shadow governments’ they appear to be a strong preference for governments looking for greater accountability of outcomes and an easier way to control the interaction with the conventional not-for-profit sector. The question is will governments’ apparent preference for larger organisational arrangements lead to the demise of the vibrancy of the not-for-profit sector and impact on service provision to those people who fall outside of the remit of the new service providers? To address this issue, this paper uses information gleaned from a state-wide survey of not-for-profit organisations in Queensland, Australia which included organisational size, operational scope, funding arrangements and governance/management approaches. Supplementing this information is qualitative data derived from 17 focus groups and 120 interviews conducted over ten years of study of this sector. The findings contribute to greater understanding of the practice and theory of the future provision of social services.

Living City 2010 Workshop

Living City 2010 was a three-day place-based urban design immersion workshop program held at Logan Road Conference Centre, Stones Corner, for 30 self-selected Year 11 Visual Art Students and 4 Teachers drawn from 11 state and private Brisbane Secondary Schools, that focused on the active Brisbane City Council redevelopment site of Stones Corner, specifically Logan Road, public spaces at Stones Corner Library and rehabilitation of the nearby creek corridor. The workshop, framed within notions of ecological, economic, social and cultural sustainability, aimed to raise awareness of the layered complexity and perspectives involved in the design of shared city spaces and to encourage young people to voice their own concerns as future citizens about the shape and direction of their city. On Day 1, Brisbane City Council Public Art Officers Brendan Doherty and Genevieve Searle, local landscape architect Peter Boyle (Verge) and artists Malcolm Enright and Barbara Heath provided students with an overview of the historic and future context of the area including proposed design and public art interventions, followed by a site walk. The afternoon session, led by Natalie Wright and QUT design staff and students, focused on design tools to assist in the tackling of the redesign of the Stones Corner library precinct, where students worked on ideas. On Day 2, students were mentored by artist Liam Key to participate in a computer animation activity using the built environment as a canvas, and by artist Sebastian Moody to participate in an activity using red helium balloons as a playful catalyst for interaction to activate and create new public space. Later, students worked in teams on their ideas for redevelopment of the site in preparation for their Day 3 presentations. The workshop culminated in an exchange of planning ideas with Georgina Aitchison from Brisbane City Council's Urban Renewal Division. Students were introduced to design methodology, team thinking strategies, the scope of design practices and professions, presentation skills and post-secondary pathways, while participating teachers acquired content and design learning strategies transferable in many other contexts.

Chongqing International Circus City

The design grows out of the rich culture of circus and the rugged dynamic topography of Chongqing. The site for this project is nestled on the banks of the mighty Yangzte, China's longest river: a vast sweeping watery ribbon carving its way through the mountainous terrain. This swirling sinuous environmental thread replicates in nature the tweisting ribbons circling the gyrating circus gymnast. The project grows from intertwining these swirling parallel conceptions of 'ribbon'. A multi-layered envelope of glass and steel ribbons creates a dome like enclosure that wraps itself around the dynamic performing heart of the circus. The main auditorium and stage area are accommodated in this space. Key public elements and facilities are located adjacent to the new riverfront boulevard maximising the positive relationship with this attractive landscape zone. Service and support areas are located along the southern boundary. Key Statistics; Client: Chongqing Broadcast Bureau Developer: Chongqing Real Estate Site: 3.3 Ha Development: Total G.F.A.: 36,800m2 Project Cost: Total Investment: RMB 300 Million (A$48 million) Other competition participants were BIG-Bjarke Ingels Group (Denmark)/arquitectonica (USA)/Beijing Architectural Design Institute/East China Architectural Design Institute/China Architectural Design Academy.

Big-five personality factors affecting driving behaviours

The factors affecting driving behaviors are various and interact simultaneously. Therefore, study of their correlations affecting on driving behaviors is of interest. This paper reports a questionnaire survey in China, focusing on the effect of Big-Five factors on speeding, drink driving, and distracted driving while Akers' social learning theory and Homel's deterrence theory were applied. The results showed that personalities had significant effect on speeding and drink driving; social factors had significant effect on speeding and distracted driving; deterrence had significant effect on speeding and drink driving; however, social learning theory did not contribute to drink driving; deterrence did not affect distracted driving. The results were discussed along with the limitation of this study.