Insights into the mechanism of the reaction between ttrachloro-p-bnzoquinone and hydrogen peroxide and their implications in the catalytic role of water molecules in producing the hydroxyl radial

Detailed mechanisms for the formation of hydroxyl or alkoxyl radicals in the reactions between tetrachloro-p-benzoquinone (TCBQ) and organic hydroperoxides are crucial for better understanding the potential carcinogenicity of polyhalogenated quinones. Herein, the mechanism of the reaction between TCBQ and H2O2 has been systematically investigated at the B3LYP/6-311++G** level of theory in the presence of different numbers of water molecules. We report that the whole reaction can easily take place with the assistance of explicit water molecules. Namely, an initial intermediate is formed first. After that, a nucleophilic attack of H2O2 onto TCBQ occurs, which results in the formation of a second intermediate that contains an OOH group. Subsequently, this second intermediate decomposes homolytically through cleavage of the O-O bond to produce a hydroxyl radical. Energy analyses suggest that the nucleophilic attack is the rate-determining step in the whole reaction. The participation of explicit water molecules promotes the reaction significantly, which can be used to explain the experimental phenomena. In addition, the effects of F, Br, and CH3 substituents on this reaction have also been studied.

Experimental and numerical study of water-filled road safety barriers

Portable water-filled road barriers (PWFB) are roadside structures placed on temporary construction zones to separate work site from moving traffic. Recent changes in governing standards require PWFB to adhere to strict compliance in terms of lateral displacement of the road barriers and vehicle redirectionality. Actual road safety barrier test can be very costly, thus researchers resort to Finite Element Analysis (FEA) in the initial designs phase prior to real vehicle test. There has been many research conducted on concrete barriers and flexible steel barriers using FEA, however not many is done pertaining to PWFB. This research probes a new method to model joint mechanism in PWFB. Two methods to model the joining mechanism are presented and discussed in relation to its practicality and accuracy to real work applications. Moreover, the study of the physical gap and mass of the barrier was investigated. Outcome from this research will benefit PWFB research and allow road barrier designers better knowledge in developing the next generation of road safety structures.

Selecting rainfall events for effective Water Sensitive Urban Design (WSUD) implementation

The current approach for protecting the receiving water environment from urban stormwater pollution is the adoption of structural measures commonly referred to as Water Sensitive Urban Design (WSUD). The treatment efficiency of WSUD measures closely depends on the design of the specific treatment units. As stormwater quality can be influenced by rainfall characteristics, the selection of appropriate rainfall events for treatment design is essential to ensure the effectiveness of WSUD systems. Based on extensive field investigation of four urban residential catchments and computer modelling, this paper details a technically robust approach for the selection of rainfall events for stormwater treatment design using a three-component model. The modelling outcomes indicate that selecting smaller average recurrence interval (ARI) events with high intensity-short duration as the threshold for the treatment system design is the most feasible since these events cumulatively generate a major portion of the annual pollutant load compared to the other types of rainfall events, despite producing a relatively smaller runoff volume. This implies that designs based on small and more frequent rainfall events rather than larger rainfall events would be appropriate in the context of efficiency in treatment performance, cost-effectiveness and possible savings in land area needed.

Synthesis, characterisation and application of organic surfactants modified clays for water purification

This thesis offered a step forward in the development of cheap and effective materials for water treatment. It described the modification of naturally abundant clay minerals with organic molecules, and used the modified clays as effective adsorbents for the removal of recalcitrant organic water pollutants. The outcome of the study greatly extended our understanding of the synthesis and characteristic properties of clay and modified clay minerals, provided optimistic evaluation of the modified clays for environmental remediation and offered potential utility for clay minerals in the industry and environment.

Quantification of ebullitive and diffusive methane release to atmosphere from a water storage

Accurately quantifying total freshwater storage methane release to atmosphere requires the spatial–temporal measurement of both diffusive and ebullitive emissions. Existing floating chamber techniques provide localised assessment of methane flux, however, significant errors can arise when weighting and extrapolation to the entire storage, particularly when ebullition is significant. An improved technique has been developed that compliments traditional chamber based experiments to quantify the storage-scale release of methane gas to atmosphere through ebullition using the measurements from an Optical Methane Detector (OMD) and a robotic boat. This provides a conservative estimate of the methane emission rate from ebullition along with the bubble volume distribution. It also georeferences the area of ebullition activity across entire storages at short temporal scales. An assessment on Little Nerang Dam in Queensland, Australia, demonstrated whole storage methane release significantly differed spatially and throughout the day. Total methane emission estimates showed a potential 32-fold variation in whole-of-dam rates depending on the measurement and extrapolation method and time of day used. The combined chamber and OMD technique showed that 1.8–7.0% of the surface area of Little Nerang Dam is accounting for up to 97% of total methane release to atmosphere throughout the day. Additionally, over 95% of detectable ebullition occurred in depths less than 12 m during the day and 6 m at night. This difference in spatial and temporal methane release rate distribution highlights the need to monitor significant regions of, if not the entire, water storage in order to provide an accurate estimate of ebullition rates and their contribution to annual methane emissions.

Continuous monitoring of reservoir water quality: The Wivenhoe Project

The Lake Wivenhoe Integrated Wireless Sensor Network is conceptually similar to traditional SCADA monitoring and control approaches. However, it is applied in an open system using wireless devices to monitor processes that affect water quality at both a high spatial and temporal frequency. This monitoring assists scientists to better understand drivers of key processes that influence water quality and provide the operators with an early warning system if below standard water enters the reservoir. Both of these aspects improve the safety and efficient delivery of drinking water to the end users.

Diffusion tensor of water in partially aligned fibre networks

Monte Carlo simulations were used to investigate the relationship between the morphological characteristics and the diffusion tensor (DT) of partially aligned networks of cylindrical fibres. The orientation distributions of the fibres in each network were approximately uniform within a cone of a given semi-angle (θ0). This semi-angle was used to control the degree of alignment of the fibres. The networks studied ranged from perfectly aligned (θ0 = 0) to completely disordered (θ0 = 90°). Our results are qualitatively consistent with previous numerical models in the overall behaviour of the DT. However, we report a non-linear relationship between the fractional anisotropy (FA) of the DT and collagen volume fraction, which is different to the findings from previous work. We discuss our results in the context of diffusion tensor imaging of articular cartilage. We also demonstrate how appropriate diffusion models have the potential to enable quantitative interpretation of the experimentally measured diffusion-tensor FA in terms of collagen fibre alignment distributions.

New catalysts for organic synthesis driven by light and efficient sorbents for removal of radioactive ions from water

The body of the thesis contained two separate elements which made an original contribution to fundamental understanding in the areas of photocatalysis, chemical synthesis and water treatment. Research on chemical reactions catalyzed by noble metal nanoparticles (such as gold) or surface complex grafted metal oxides which can be driven by sunlight at ambient temperature and the second element on radioactive cesium (137Cs+) cations and iodine (125I-) anions recovery by the unique structural features of titanate nanostructures for firmly capture and safe storage; the works has been all published in journals that are rated at the top of their respective fields.

An investigation of silver electrodeposition from ionic liquids : influence of atmospheric water uptake on the silver electrodeposition mechanism and film morphology

The electrodeposition of silver from two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4mPyr][TFSI]), and an aqueous KNO3 solution on a glassy carbon electrode was undertaken. It was found by cyclic voltammetry that the electrodeposition of silver proceeds through nucleation–growth kinetics. Analysis of chronoamperometric data indicated that the nucleation–growth mechanism is instantaneous at all potentials in the case of [BMIm][BF4] and [C4mPyr][TFSI], and instantaneous at low overpotentials tending to progressive at high overpotentials for KNO3. Significantly, under ambient conditions, the silver electrodeposition mechanism changes to progressive nucleation and growth in [C4mPyr][TFSI], which is attributed to the uptake of atmospheric water in the IL. It was found that these differences in the growth mechanism impact significantly on the morphology of the resultant electrodeposit which is characterised ex situ by scanning electron microscopy and X-ray diffraction.

Rating for sustainable subdivision neighbourhood design (RSSND) : case of Bangkok metropolitan region (BMR), Thailand an eco-efficiency modelling approach

Bangkok Metropolitan Region (BMR) is the centre for various major activities in Thailand including political, industry, agriculture, and commerce. Consequently, the BMR is the highest and most densely populated area in Thailand. Thus, the demand for houses in the BMR is also the largest, especially in subdivision developments. For these reasons, the subdivision development in the BMR has increased substantially in the past 20 years and generated large numbers of subdivision developments (AREA, 2009; Kridakorn Na Ayutthaya & Tochaiwat, 2010). However, this dramatic growth of subdivision development has caused several problems including unsustainable development, especially for subdivision neighbourhoods, in the BMR. There have been rating tools that encourage the sustainability of neighbourhood design in subdivision development, but they still have practical problems. Such rating tools do not cover the scale of the development entirely; and they concentrate more on the social and environmental conservation aspects, which have not been totally accepted by the developers (Boonprakub, 2011; Tongcumpou & Harvey, 1994). These factors strongly confirm the need for an appropriate rating tool for sustainable subdivision neighbourhood design in the BMR. To improve level of acceptance from all stakeholders in subdivision developments industry, the new rating tool should be developed based on an approach that unites the social, environmental, and economic approaches, such as eco-efficiency principle. Eco-efficiency is the sustainability indicator introduced by the World Business Council for Sustainable Development (WBCSD) since 1992. The eco-efficiency is defined as the ratio of the product or service value according to its environmental impact (Lehni & Pepper, 2000; Sorvari et al., 2009). Eco-efficiency indicator is concerned to the business, while simultaneously, is concerned with to social and the environment impact. This study aims to develop a new rating tool named "Rating for sustainable subdivision neighbourhood design (RSSND)". The RSSND methodology is developed by a combination of literature reviews, field surveys, the eco-efficiency model development, trial-and-error technique, and the tool validation process. All required data has been collected by the field surveys from July to November 2010. The ecoefficiency model is a combination of three different mathematical models; the neighbourhood property price (NPP) model, the neighbourhood development cost (NDC) model, and the neighbourhood occupancy cost (NOC) model which are attributable to the neighbourhood subdivision design. The NPP model is formulated by hedonic price model approach, while the NDC model and NOC model are formulated by the multiple regression analysis approach. The trial-and-error technique is adopted for simplifying the complex mathematic eco-efficiency model to a user-friendly rating tool format. Credibility of the RSSND has been validated by using both rated and non-rated of eight subdivisions. It is expected to meet the requirements of all stakeholders which support the social activities of the residents, maintain the environmental condition of the development and surrounding areas, and meet the economic requirements of the developers.

Engaging young people : reflections from a participatory water planning exercise

While participatory processes have become an important part of water planning, young people are a particularly vulnerable group in terms of potential marginalisation and exclusion from effective participation. Including the views of young people in water planning is not simply a matter of bringing them into existing processes. Instead, processes must be modified to accommodate their needs and ways of expressing their views. Without these adjustments young people may simply move from being kept outside the process to a situation where although they are formally included, their claims are not taken seriously and they are not treated with equal respect. In this paper we reflect on the success of the community advisory committee, formed to develop the Gold Coast Waterfuture Strategy, in integrating the views of young people into their deliberations. Using Young's communicative democracy we highlight the challenges and opportunities presented by this approach, as articulated by both the young people involved and the adult participants, and specifically consider the how the elements of greeting, rhetoric and narrative were reflected in the committee process.

Experiences of regional and rural people with cancer being treated with radiotherapy in a metropolitan centre

This paper explores the issues related to rural people with cancer whose choice of radiotherapy treatment necessitated travel and accommodation in a metropolitan centre. Semi-structured interviews with 46 participants, from the Toowoomba and Darling Downs region of Queensland, Australia, were conducted and the data thematically analysed. The specific themes identified were: being away from loved ones, maintaining responsibilities whilst undergoing treatment, emotional stress, burden on significant others, choice about radiotherapy as a treatment, travel and accommodation, and financial burden. This study supports the need for a radiotherapy centre in the location of Toowoomba as a way of providing some equity and access to such treatment for the rural people of Queensland.

Better understanding of food material on the basis of water distribution using Thermogravimetric analysis

The prime objective of drying is to enhance shelf life of perishable food materials. As the process is very energy intensive in nature, researchers are trying to minimise energy consumption in the drying process. In order to determine the exact amount of energy needed for drying a food product, understanding the physics of moisture distribution and bond strength of water within the food material is essential. In order understand the critical moisture content, moisture distribution and water bond strength in food material, Thermogravimetric analysis (TGA) can be properly utilised. This work has been conducted to investigate moisture distribution and water bond strength in selected food materials; apple, banana and potato. It was found that moisture distribution and water bond strength influence moisture migration from the food materials. In addition, proportion of different types of water (bound, free, surface water) has been simply identified using TGA. This study provides a better understanding of water contents and its role in drying rate and energy consumption.

Vision in water

The purpose of this study is to determine visual performance in water, including the influence of pupil size. The water en-vironment was simulated by placing a goggle filled with saline in front of eyes, with apertures placed at the front of the goggle. Correction factors were determined for the different magnification under this condition in order to to estimate vision in water. Experiments were conducted on letter visual acuity (7 participants), grating resolution (8 participants), and grating contrast sensitivity (1 participant). For letter acuity, mean loss in vision in water, compared to corrected vision in air, varied between 1.1 log minutes of arc resolution (logMAR) for a 1mm aperture to 2.2 logMAR for a 7mm aperture. The vision in minutes of arc was described well by a linear relationship with pupil size. For grating acuity, mean loss varied between 1.1 logMAR for a 2mm aperture to 1.2 logMAR for a 6mm aperture. Contrast sensitivity for a 2mm aperture dete-riorated as spatial frequency increased, with 2 log unit loss by 3 cycles/degree. Superimposed on this deterioration were depressions (notches) in sensitivity, with the first three notches occurring at 0.45, 0.8 and 1.3 cycles/degree with esti-mates for water of 0.39, 0.70 and 1.13 cycles/degree. In conclusion, vision in water is poor. It becomes worse as pupil size increases, but the effects are much more marked for letter targets than for grating targets.