Investigating variation in bus ridership rates within localised areas of a sub-tropical city

This thesis makes a significant contribution to knowledge and understanding of 'Human Travel Behaviour' in relation to transportation research. It holds some important merits that have not been proposed before. It develops a new, comprehensive and meaningful relationship that includes bus transit ridership change due to weather variables, seasonality and transit quality of service within a single daily ridership rate estimation model. The research incorporated both temporal and spatial influences on ridership within a modelling structure, named as the Nested Model Structure. It provides a complete picture of ridership variation across the sub-tropical city of Brisbane, Australia.

Nano-confined synthesis of highly ordered mesoporous carbon and its performance as electrode material for electrochemical behavior of riboflavin (vitamin B2) and dopamine

Highly ordered mesoporous carbon (MC) has been synthesized from sucrose, a non-toxic and costeffective source of carbon. X-ray diffraction, N2 adsorption–desorption isotherm and transmission electron micrograph (TEM) were used to characterize the MC. The XRD patterns show the formation of highly ordered mesoporous structures of SBA15 and mesoporous carbon. The N2 adsorptiondesorption isotherms suggest that the MC exhibits a narrow pore-size distribution with high surface area of 1559 m2/g. The potential application of MC as a novel electrode material was investigated using cyclic voltammetry for riboflavin (vitamin B2) and dopamine. MC-modified glassy carbon electrode (MC/GC) shows increase in peak current compared to GC electrode in potassium ferricyanide which clearly suggest that MC/GC possesses larger electrode area (1.8 fold) compared with bare GC electrode. The electrocatalytic behavior of MC/GC was investigated towards the oxidation of riboflavin (vitamin B2) and dopamine using cyclic voltammetry which show larger oxidation current compared to unmodified electrode and thus MC/GC may have the potential to be used as a chemically modified electrode.

New organisational leadership capabilities : transitional engineer the new designer?

Traditionally, design has been centred within the manufacturing and production areas of companies and or as a styling afterthought. Increasingly, design is viewed as a vital and important strategic business resource (Dell’Era, Marchesi & Verganti, 2010) and consequently companies worldwide look to design to help them innovate, differentiate and compete in the global marketplace. The role of the professional designer is evolving to a point where they are needed to work beyond being a specialist in the manufacturing and aesthetics of an artefact (Wrigley & Bucolo, 2011). This paper challenges the values held by academics and industry regarding the traditional role of designers in business. It investigates the emerging transitional engineering framework and puts forward a proposal for the next generation designer in the future era of design. Questions surrounding how designers will develop these new skills and how the Authors’ new framework of design led innovation can contribute to the future of design will be presented. This research is needed to better equip future designers to have a more central role in business.

N2O emissions from agricultural lands: a synthesis of simulation approaches

Nitrous oxide (N2O) is primarily produced by the microbially-mediated nitrification and denitrification processes in soils. It is influenced by a suite of climate (i.e. temperature and rainfall) and soil (physical and chemical) variables, interacting soil and plant nitrogen (N) transformations (either competing or supplying substrates) as well as land management practices. It is not surprising that N2O emissions are highly variable both spatially and temporally. Computer simulation models, which can integrate all of these variables, are required for the complex task of providing quantitative determinations of N2O emissions. Numerous simulation models have been developed to predict N2O production. Each model has its own philosophy in constructing simulation components as well as performance strengths. The models range from those that attempt to comprehensively simulate all soil processes to more empirical approaches requiring minimal input data. These N2O simulation models can be classified into three categories: laboratory, field and regional/global levels. Process-based field-scale N2O simulation models, which simulate whole agroecosystems and can be used to develop N2O mitigation measures, are the most widely used. The current challenge is how to scale up the relatively more robust field-scale model to catchment, regional and national scales. This paper reviews the development history, main construction components, strengths, limitations and applications of N2O emissions models, which have been published in the literature. The three scale levels are considered and the current knowledge gaps and challenges in modelling N2O emissions from soils are discussed.

The influence of climate variability on hydrological processes and surface and groundwater hydrochemistry : the tropical upper roper river catchment, Northern Territory, Australia

The Upper Roper River is one of the Australia’s unique tropical rivers which have been largely untouched by development. The Upper Roper River catchment comprises the sub-catchments of the Waterhouse River and Roper Creek, the two tributaries of the Roper River. There is a complex geological setting with different aquifer types. In this seasonal system, close interaction between surface water and groundwater contributes to both streamflow and sustaining ecosystems. The interaction is highly variable between seasons. A conceptual hydrogeological model was developed to investigate the different hydrological processes and geochemical parameters, and determine the baseline characteristics of water resources of this pristine catchment. In the catchment, long term average rainfall is around 850 mm and is summer dominant which significantly influences the total hydrological system. The difference between seasons is pronounced, with high rainfall up to 600 mm/month in the wet season, and negligible rainfall in the dry season. Canopy interception significantly reduces the amount of effective rainfall because of the native vegetation cover in the pristine catchment. Evaporation exceeds rainfall the majority of the year. Due to elevated evaporation and high temperature in the tropics, at least 600 mm of annual rainfall is required to generate potential recharge. Analysis of 120 years of rainfall data trend helped define “wet” and “dry periods”: decreasing trend corresponds to dry periods, and increasing trend to wet periods. The period from 1900 to 1970 was considered as Dry period 1, when there were years with no effective rainfall, and if there was, the intensity of rainfall was around 300 mm. The period 1970 – 1985 was identified as the Wet period 2, when positive effective rainfall occurred in almost every year, and the intensity reached up to 700 mm. The period 1985 – 1995 was the Dry period 2, with similar characteristics as Dry period 1. Finally, the last decade was the Wet period 2, with effective rainfall intensity up to 800 mm. This variability in rainfall over decades increased/decreased recharge and discharge, improving/reducing surface water and groundwater quantity and quality in different wet and dry periods. The stream discharge follows the rainfall pattern. In the wet season, the aquifer is replenished, groundwater levels and groundwater discharge are high, and surface runoff is the dominant component of streamflow. Waterhouse River contributes two thirds and Roper Creek one third to Roper River flow. As the dry season progresses, surface runoff depletes, and groundwater becomes the main component of stream flow. Flow in Waterhouse River is negligible, the Roper Creek dries up, but the Roper River maintains its flow throughout the year. This is due to the groundwater and spring discharge from the highly permeable Tindall Limestone and tufa aquifers. Rainfall seasonality and lithology of both the catchment and aquifers are shown to influence water chemistry. In the wet season, dilution of water bodies by rainwater is the main process. In the dry season, when groundwater provides baseflow to the streams, their chemical composition reflects lithology of the aquifers, in particular the karstic areas. Water chemistry distinguishes four types of aquifer materials described as alluvium, sandstone, limestone and tufa. Surface water in the headwaters of the Waterhouse River, the Roper Creek and their tributaries are freshwater, and reflect the alluvium and sandstone aquifers. At and downstream of the confluence of the Roper River, river water chemistry indicates the influence of rainfall dilution in the wet season, and the signature of the Tindall Limestone and tufa aquifers in the dry. Rainbow Spring on the Waterhouse River and Bitter Spring on the Little Roper River (known as Roper Creek at the headwaters) discharge from the Tindall Limestone. Botanic Walk Spring and Fig Tree Spring discharge into the Roper River from tufa. The source of water was defined based on water chemical composition of the springs, surface and groundwater. The mechanisms controlling surface water chemistry were examined to define the dominance of precipitation, evaporation or rock weathering on the water chemical composition. Simple water balance models for the catchment have been developed. The important aspects to be considered in water resource planning of this total system are the naturally high salinity in the region, especially the downstream sections, and how unpredictable climate variation may impact on the natural seasonal variability of water volumes and surface-subsurface interaction.

The geostationary orbit : a critical legal geography of space’s most valuable real estate

This chapter attends to the legal and political geographies of one of Earth's most important, valuable, and pressured spaces: the geostationary orbit. Since the first, NASA, satellite entered it in 1964, this small, defined band of Outer Space, 35,786km from the Earth's surface, and only 30km wide, has become a highly charged legal and geopolitical environment, yet it remains a space which is curiously unheard of outside of specialist circles. For the thousands of satellites which now underpin the Earth's communication, media, and data industries and flows, the geostationary orbit is the prime position in Space. The geostationary orbit only has the physical capacity to hold approximately 1500 satellites; in 1997 there were approximately 1000. It is no overstatement to assert that media, communication, and data industries would not be what they are today if it was not for the geostationary orbit. This chapter provides a critical legal geography of the geostationary orbit, charting the topography of the debates and struggles to define and manage this highly-important space. Drawing on key legal documents such as the Outer Space Treaty and the Moon Treaty, the chapter addresses fundamental questions about the legal geography of the orbit, questions which are of growing importance as the orbit’s available satellite spaces diminish and the orbit comes under increasing pressure. Who owns the geostationary orbit? Who, and whose rules, govern what may or may not (literally) take place within it? Who decides which satellites can occupy the orbit? Is the geostationary orbit the sovereign property of the equatorial states it supertends, as these states argued in the 1970s? Or is it a part of the res communis, or common property of humanity, which currently legally characterises Outer Space? As challenges to the existing legal spatiality of the orbit from launch states, companies, and potential launch states, it is particularly critical that the current spatiality of the orbit is understood and considered. One of the busiest areas of Outer Space’s spatiality is international territorial law. Mentions of Space law tend to evoke incredulity and ‘little green men’ jokes, but as Space becomes busier and busier, international Space law is growing in complexity and importance. The chapter draws on two key fields of research: cultural geography, and critical legal geography. The chapter is framed by the cultural geographical concept of ‘spatiality’, a term which signals the multiple and dynamic nature of geographical space. As spatial theorists such as Henri Lefebvre assert, a space is never simply physical; rather, any space is always a jostling composite of material, imagined, and practiced geographies (Lefebvre 1991). The ways in which a culture perceives, represents, and legislates that space are as constitutive of its identity--its spatiality--as the physical topography of the ground itself. The second field in which this chapter is situated—critical legal geography—derives from cultural geography’s focus on the cultural construction of spatiality. In his Law, Space and the Geographies of Power (1994), Nicholas Blomley asserts that analyses of territorial law largely neglect the spatial dimension of their investigations; rather than seeing the law as a force that produces specific kinds of spaces, they tend to position space as a neutral, universally-legible entity which is neatly governed by the equally neutral 'external variable' of territorial law (28). 'In the hegemonic conception of the law,' Pue similarly argues, 'the entire world is transmuted into one vast isotropic surface' (1990: 568) on which law simply acts. But as the emerging field of critical legal geography demonstrates, law is not a neutral organiser of space, but is instead a powerful cultural technology of spatial production. Or as Delaney states, legal debates are “episodes in the social production of space” (2001, p. 494). International territorial law, in other words, makes space, and does not simply govern it. Drawing on these tenets of the field of critical legal geography, as well as on Lefebvrian concept of multipartite spatiality, this chapter does two things. First, it extends the field of critical legal geography into Space, a domain with which the field has yet to substantially engage. Second, it demonstrates that the legal spatiality of the geostationary orbit is both complex and contested, and argues that it is crucial that we understand this dynamic legal space on which the Earth’s communications systems rely.

Apple skin patterning is associated with differential expression of MYb10

Background Some apple (Malus × domestica Borkh.) varieties have attractive striping patterns, a quality attribute that is important for determining apple fruit market acceptance. Most apple cultivars (e.g. 'Royal Gala') produce fruit with a defined fruit pigment pattern, but in the case of 'Honeycrisp' apple, trees can produce fruits of two different kinds: striped and blushed. The causes of this phenomenon are unknown. Results Here we show that striped areas of 'Honeycrisp' and 'Royal Gala' are due to sectorial increases in anthocyanin concentration. Transcript levels of the major biosynthetic genes and MYB10, a transcription factor that upregulates apple anthocyanin production, correlated with increased anthocyanin concentration in stripes. However, nucleotide changes in the promoter and coding sequence of MYB10 do not correlate with skin pattern in 'Honeycrisp' and other cultivars differing in peel pigmentation patterns. A survey of methylation levels throughout the coding region of MYB10 and a 2.5 Kb region 5' of the ATG translation start site indicated that an area 900 bp long, starting 1400 bp upstream of the translation start site, is highly methylated. Cytosine methylation was present in all three contexts, with higher methylation levels observed for CHH and CHG (where H is A, C or T) than for CG. Comparisons of methylation levels of the MYB10 promoter in 'Honeycrisp' red and green stripes indicated that they correlate with peel phenotypes, with an enrichment of methylation observed in green stripes. Conclusions Differences in anthocyanin levels between red and green stripes can be explained by differential transcript accumulation of MYB10. Different levels of MYB10 transcript in red versus green stripes are inversely associated with methylation levels in the promoter region. Although observed methylation differences are modest, trends are consistent across years and differences are statistically significant. Methylation may be associated with the presence of a TRIM retrotransposon within the promoter region, but the presence of the TRIM element alone cannot explain the phenotypic variability observed in 'Honeycrisp'. We suggest that methylation in the MYB10 promoter is more variable in 'Honeycrisp' than in 'Royal Gala', leading to more variable color patterns in the peel of this cultivar.

Simulation and development of a mock circulation loop with variable compliance

Heart disease is attributed as the highest cause of death in the world. Although this could be alleviated by heart transplantation, there is a chronic shortage of donor hearts and so mechanical solutions are being considered. Currently, many Ventricular Assist Devices (VADs) are being developed worldwide in an effort to increase life expectancy and quality of life for end stage heart failure patients. Current pre-clinical testing methods for VADs involve laboratory testing using Mock Circulation Loops (MCLs), and in vivo testing in animal models. The research and development of highly accurate MCLs is vital to the continuous improvement of VAD performance. The first objective of this study was to develop and validate a mathematical model of a MCL. This model could then be used in the design and construction of a variable compliance chamber to improve the performance of an existing MCL as well as form the basis for a new miniaturised MCL. An extensive review of literature was carried out on MCLs and mathematical modelling of their function. A mathematical model of a MCL was then created in the MATLAB/SIMULINK environment. This model included variable features such as resistance, fluid inertia and volumes (resulting from the pipe lengths and diameters); compliance of Windkessel chambers, atria and ventricles; density of both fluid and compressed air applied to the system; gravitational effects on vertical columns of fluid; and accurately modelled actuators controlling the ventricle contraction. This model was then validated using the physical properties and pressure and flow traces produced from a previously developed MCL. A variable compliance chamber was designed to reproduce parameters determined by the mathematical model. The function of the variability was achieved by controlling the transmural pressure across a diaphragm to alter the compliance of the system. An initial prototype was tested in a previously developed MCL, and a variable level of arterial compliance was successfully produced; however, the complete range of compliance values required for accurate physiological representation was not able to be produced with this initial design. The mathematical model was then used to design a smaller physical mock circulation loop, with the tubing sizes adjusted to produce accurate pressure and flow traces whilst having an appropriate frequency response characteristic. The development of the mathematical model greatly assisted the general design of an in vitro cardiovascular device test rig, while the variable compliance chamber allowed simple and real-time manipulation of MCL compliance to allow accurate transition between a variety of physiological conditions. The newly developed MCL produced an accurate design of a mechanical representation of the human circulatory system for in vitro cardiovascular device testing and education purposes. The continued improvement of VAD test rigs is essential if VAD design is to improve, and hence improve quality of life and life expectancy for heart failure patients.

An identification of factors influencing police workplace motivation

Police work tasks are diverse and require the ability to take command, demonstrate leadership, make serious decisions and be self directed (Beck, 1999; Brunetto & Farr-Wharton, 2002; Howard, Donofrio & Boles, 2002). This work is usually performed in pairs or sometimes by an officer working alone. Operational police work is seldom performed under the watchful eyes of a supervisor and a great amount of reliance is placed on the high levels of motivation and professionalism of individual officers. Research has shown that highly motivated workers produce better outcomes (Whisenand & Rush, 1998; Herzberg, 2003). It is therefore important that Queensland police officers are highly motivated to provide a quality service to the Queensland community. This research aims to identify factors which motivate Queensland police to perform quality work. Researchers acknowledge that there is a lack of research and knowledge in regard to the factors which motivate police (Beck, 1999; Bragg, 1998; Howard, Donofrio & Boles, 2002; McHugh & Verner, 1998). The motivational factors were identified in regard to the demographic variables of; age, sex, rank, tenure and education. The model for this research is Herzberg’s two-factor theory of workplace motivation (1959). Herzberg found that there are two broad types of workplace motivational factors; those driven by a need to prevent loss or harm and those driven by a need to gain personal satisfaction or achievement. His study identified 16 basic sub-factors that operate in the workplace. The research utilised a questionnaire instrument based on the sub-factors identified by Herzberg (1959). The questionnaire format consists of an initial section which sought demographic information about the participant and is followed by 51 Likert scale questions. The instrument is an expanded version of an instrument previously used in doctoral studies to identify sources of police motivation (Holden, 1980; Chiou, 2004). The questionnaire was forwarded to approximately 960 police in the Brisbane, Metropolitan North Region. The data were analysed using Factor Analysis, MANOVAs, ANOVAs and multiple regression analysis to identify the key sources of police motivation and to determine the relationships between demographic variables such as: age, rank, educational level, tenure, generation cohort and motivational factors. A total of 484 officers responded to the questionnaire from the sample population of 960. Factor analysis revealed five broad Prime Motivational Factors that motivate police in their work. The Prime Motivational Factors are: Feeling Valued, Achievement, Workplace Relationships, the Work Itself and Pay and Conditions. The factor Feeling Valued highlighted the importance of positive supportive leaders in motivating officers. Many officers commented that supervisors who only provided negative feedback diminished their sense of feeling valued and were a key source of de-motivation. Officers also frequently commented that they were motivated by operational police work itself whilst demonstrating a strong sense of identity with their team and colleagues. The study showed a general need for acceptance by peers and an idealistic motivation to assist members of the community in need and protect victims of crime. Generational cohorts were not found to exert a significant influence on police motivation. The demographic variable with the single greatest influence on police motivation was tenure. Motivation levels were found to drop dramatically during the first two years of an officer’s service and generally not improve significantly until near retirement age. The findings of this research provide the foundation of a number of recommendations in regard to police retirement, training and work allocation that are aimed to improve police motivation levels. The five Prime Motivational Factor model developed in this study is recommended for use as a planning tool by police leaders to improve motivational and job-satisfaction components of police Service policies. The findings of this study also provide a better understanding of the current sources of police motivation. They are expected to have valuable application for Queensland police human resource management when considering policies and procedures in the areas of motivation, stress reduction and attracting suitable staff to specific areas of responsibility.

Genetic resources in wild and cultured stocks of the Asian mud crab, Scylla paramamosain

The mud crab (Scylla spp.) aquaculture industry has expanded rapidly in recent years in many countries in the Indo - West Pacific (IWP) region as an alternative to marine shrimp culture because of significant disease outbreaks and associated failures of many shrimp culture industries in the region. Currently, practices used to produce and manage breeding crabs in hatcheries may compromise levels of genetic diversity, ultimately compromising growth rates, disease resistance and stock productivity. Therefore, to avoid “genetic pollution” and its harmful effects and to promote further development of mud crab aquaculture and fisheries in a sustainable way, a greater understanding of the genetic attributes of wild and cultured mud crab stocks is required. Application of these results can provide benefits for managing wild and cultured Asian mud crab populations for multiple purposes including for commercial production, recreation and conservation and to increase profitability and sustainability of newly emerging crab culture industries. Phylogeographic patterns and the genetic structure of Asian mud crab populations across the IWP were assessed to determine if they were concordant with those of other widespread taxa possessing pelagic larvae of relatively long duration. A 597 bp fragment of the mitochondrial DNA COI gene was amplified and screened for variation in a total of 297 individuals of S. paramamosain from six sampling sites across the species’ natural geographical distribution in the IWP and 36 unique haplotypes were identified. Haplotype diversities per site ranged from 0.516 to 0.879. Nucleotide diversity estimates among haplotypes were 0.11% – 0.48%. Maximum divergence observed among S. paramamosain samples was 1.533% and samples formed essentially a single monophyletic group as no obvious clades were related to geographical location of sites. A weak positive relationship was observed however, between genetic distance and geographical distance among sites. Microsatellite markers were then used to assess contemporary gene flow and population structure in Asian mud crab populations sampled across their natural distribution in the IWP. Eight microsatellite loci were screened in sampled S. paramamosain populations and all showed high allelic diversity at all loci in sampled populations. In total, 344 individuals were analysed, and 304 microsatellite alleles were found across the 8 loci. The mean number of alleles per locus at each site ranged from 20.75 to 28.25. Mean allelic richness per site varied from 17.2 to 18.9. All sites showed high levels of heterozygosity as average expected heterozygosities for all loci ranged from 0.917 – 0.953 while mean observed heterozygosity ranged from 0.916 – 0.959. Allele diversities were similar at all sites and across all loci. The results did not show any evidence for major differences in allele frequencies among sites and patterns of allele frequencies were very similar in all populations across all loci. Estimates of population differentiation (FST) were relatively low and most probably largely reflect intra – individual variation for very highly variable loci. Results from nDNA analysis showed evidence for only very limited population genetic structure among sampled S. paramamosain, and a positive and significant association for genetic and geographical distance among sample sites. Microsatellite markers were then employed to determine if adequate levels of genetic diversity has been captured in crab hatcheries for the breeding cycle. The results showed that all microsatellite loci were polymorphic in hatchery samples. Culture populations were in general, highly genetically depauperate, compared with comparable wild populations, with only 3 to 8 alleles recorded for the same loci set per population. In contrast, very high numbers of alleles per locus were found in reference wild S. paramamosain populations, which ranged from 18 to 46 alleles per locus per population. In general, this translates into a 3 to 10 fold decline in mean allelic richness per locus in all culture stocks compared with wild reference counterparts. Furthermore, most loci in all cultured S. paramamosain samples showed departures from HWE equilibrium. Allele frequencies were very different in culture samples from that present in comparable wild reference samples and this in particular, was reflected in a large decline in allele diversity per locus. The pattern observed was best explained by significant impacts of breeding practices employed in hatcheries rather than natural differentiation among wild populations used as the source of brood stock. Recognition of current problems and management strategies for the species both for the medium and long-term development of the new culture industry are discussed. The priority research to be undertaken over the medium term for S. paramamosain should be to close the life cycle fully to allow individuals to be bred on demand and their offspring equalised to control broodstock reproductive contributions. Establishing a broodstock register and pedigree mating system will be required before any selection program is implemented. This will ensure that sufficient genetic variation will be available to allow genetic gains to be sustainably achieved in a future stock improvement program. A fundamental starting point to improve hatchery practices will be to encourage farmers and hatchery managers to spawn more females in their hatcheries as it will increase background genetic diversity in culture stocks. Combining crablet cohorts from multiple hatcheries into a single cohort for supply to farmers or rotation of breeding females regularly in hatcheries will help to address immediate genetic diversity problems in culture stocks. Application of these results can provide benefits for managing wild and cultured Asian mud crab populations more efficiently. Over the long-term, application of data on genetic diversity in wild and cultured stocks of Asian mud crab will contribute to development of sustainable and productive culture industries in Vietnam and other countries in the IWP and can contribute towards conservation of wild genetic resources.

Alkaline hydrothermal treatment of titanate nanostructures

Since its initial proposal in 1998, alkaline hydrothermal processing has rapidly become an established technology for the production of titanate nanostructures. This simple, highly reproducible process has gained a strong research following since its conception. However, complete understanding and elucidation of nanostructure phase and formation have not yet been achieved. Without fully understanding phase, formation, and other important competing effects of the synthesis parameters on the final structure, the maximum potential of these nanostructures cannot be obtained. Therefore this study examined the influence of synthesis parameters on the formation of titanate nanostructures produced by alkaline hydrothermal treatment. The parameters included alkaline concentration, hydrothermal temperature, the precursor material‘s crystallite size and also the phase of the titanium dioxide precursor (TiO2, or titania). The nanostructure‘s phase and morphology was analysed using X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy (XPS), dynamic light scattering (non-invasive backscattering), nitrogen sorption, and Rietveld analysis were used to determine phase, for particle sizing, surface area determinations, and establishing phase concentrations, respectively. This project rigorously examined the effect of alkaline concentration and hydrothermal temperature on three commercially sourced and two self-prepared TiO2 powders. These precursors consisted of both pure- or mixed-phase anatase and rutile polymorphs, and were selected to cover a range of phase concentrations and crystallite sizes. Typically, these precursors were treated with 5–10 M sodium hydroxide (NaOH) solutions at temperatures between 100–220 °C. Both nanotube and nanoribbon morphologies could be produced depending on the combination of these hydrothermal conditions. Both titania and titanate phases are comprised of TiO6 units which are assembled in different combinations. The arrangement of these atoms affects the binding energy between the Ti–O bonds. Raman spectroscopy and XPS were therefore employed in a preliminary study of phase determination for these materials. The change in binding energy from a titania to a titanate binding energy was investigated in this study, and the transformation of titania precursor into nanotubes and titanate nanoribbons was directly observed by these methods. Evaluation of the Raman and XPS results indicated a strengthening in the binding energies of both the Ti (2p3/2) and O (1s) bands which correlated to an increase in strength and decrease in resolution of the characteristic nanotube doublet observed between 320 and 220 cm.1 in the Raman spectra of these products. The effect of phase and crystallite size on nanotube formation was examined over a series of temperatures (100.200 �‹C in 20 �‹C increments) at a set alkaline concentration (7.5 M NaOH). These parameters were investigated by employing both pure- and mixed- phase precursors of anatase and rutile. This study indicated that both the crystallite size and phase affect nanotube formation, with rutile requiring a greater driving force (essentially �\harsher. hydrothermal conditions) than anatase to form nanotubes, where larger crystallites forms of the precursor also appeared to impede nanotube formation slightly. These parameters were further examined in later studies. The influence of alkaline concentration and hydrothermal temperature were systematically examined for the transformation of Degussa P25 into nanotubes and nanoribbons, and exact conditions for nanostructure synthesis were determined. Correlation of these data sets resulted in the construction of a morphological phase diagram, which is an effective reference for nanostructure formation. This morphological phase diagram effectively provides a .recipe book�e for the formation of titanate nanostructures. Morphological phase diagrams were also constructed for larger, near phase-pure anatase and rutile precursors, to further investigate the influence of hydrothermal reaction parameters on the formation of titanate nanotubes and nanoribbons. The effects of alkaline concentration, hydrothermal temperature, crystallite phase and size are observed when the three morphological phase diagrams are compared. Through the analysis of these results it was determined that alkaline concentration and hydrothermal temperature affect nanotube and nanoribbon formation independently through a complex relationship, where nanotubes are primarily affected by temperature, whilst nanoribbons are strongly influenced by alkaline concentration. Crystallite size and phase also affected the nanostructure formation. Smaller precursor crystallites formed nanostructures at reduced hydrothermal temperature, and rutile displayed a slower rate of precursor consumption compared to anatase, with incomplete conversion observed for most hydrothermal conditions. The incomplete conversion of rutile into nanotubes was examined in detail in the final study. This study selectively examined the kinetics of precursor dissolution in order to understand why rutile incompletely converted. This was achieved by selecting a single hydrothermal condition (9 M NaOH, 160 °C) where nanotubes are known to form from both anatase and rutile, where the synthesis was quenched after 2, 4, 8, 16 and 32 hours. The influence of precursor phase on nanostructure formation was explicitly determined to be due to different dissolution kinetics; where anatase exhibited zero-order dissolution and rutile second-order. This difference in kinetic order cannot be simply explained by the variation in crystallite size, as the inherent surface areas of the two precursors were determined to have first-order relationships with time. Therefore, the crystallite size (and inherent surface area) does not affect the overall kinetic order of dissolution; rather, it determines the rate of reaction. Finally, nanostructure formation was found to be controlled by the availability of dissolved titanium (Ti4+) species in solution, which is mediated by the dissolution kinetics of the precursor.

The contribution of maize cropping in the Midwest USA to global warming: A regional estimate

Agricultural soils emit about 50% of the global flux of N2O attributable to human influence, mostly in response to nitrogen fertilizer use. Recent evidence that the relationship between N2O fluxes and N-fertilizer additions to cereal maize are non-linear provides an opportunity to estimate regional N2O fluxes based on estimates of N application rates rather than as a simple percentage of N inputs as used by the Intergovernmental Panel on Climate Change (IPCC). We combined a simple empirical model of N2O production with the SOCRATES soil carbon dynamics model to estimate N2O and other sources of Global Warming Potential (GWP) from cereal maize across 19,000 cropland polygons in the North Central Region (NCR) of the US over the period 1964–2005. Results indicate that the loading of greenhouse gases to the atmosphere from cereal maize production in the NCR was 1.7 Gt CO2e, with an average 268 t CO2e produced per tonne of grain. From 1970 until 2005, GHG emissions per unit product declined on average by 2.8 t CO2e ha−1 annum−1, coinciding with a stabilisation in N application rate and consistent increases in grain yield from the mid-1970’s. Nitrous oxide production from N fertilizer inputs represented 59% of these emissions, soil C decline (0–30 cm) represented 11% of total emissions, with the remaining 30% (517 Mt) from the combustion of fuel associated with farm operations. Of the 126 Mt of N fertilizer applied to cereal maize from 1964 to 2005, we estimate that 2.2 Mt N was emitted as N2O when using a non-linear response model, equivalent to 1.75% of the applied N.

Relationships between rainfall intensity, duration and suspended particle washoff from an urban road surface

A basic understanding of the relationships between rainfall intensity, duration of rainfall and the amount of suspended particles in stormwater runoff generated from road surfaces has been gained mainly from past washoff experiments using rainfall simulators. Simulated rainfall was generally applied at constant intensities, whereas rainfall temporal patterns during actual storms are typically highly variable. This paper discusses a rationale for the application of the constant-intensity washoff concepts to actual storm event runoff. The rationale is tested using suspended particle load data collected at a road site located in Toowoomba, Australia. Agreement between the washoff concepts and measured data is most consistent for intermediate-duration storms (duration <5 h and >1 h). Particle loads resulting from these storm events increase linearly with average rainfall intensity. Above a threshold intensity, there is evidence to suggest a constant or plateau particle load is reached. The inclusion of a peak discharge factor (maximum 6 min rainfall intensity) enhances the ability to predict particle loads.