Modelling photochemical production of fine particulates in a toluene/NOx/water vapour system

This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0

A study of water binding, mobility and dehydration in contact lens hydrogels using NMR

Hydrogel polymers are used for the manufacture of soft (or disposable) contact lenses worldwide today, but have a tendency to dehydrate on the eye. In vitro methods that can probe the potential for a given hydrogel polymer to dehydrate in vivo are much sought after. Nuclear magnetic resonance (NMR) has been shown to be effective in characterising water mobility and binding in similar systems (Barbieri, Quaglia et al., 1998, Larsen, Huff et al., 1990, Peschier, Bouwstra et al., 1993), predominantly through measurement of the spin-lattice relaxation time (T1), the spinspin relaxation time (T2) and the water diffusion coefficient (D). The aim of this work was to use NMR to quantify the molecular behaviour of water in a series of commercially available contact lens hydrogels, and relate these measurements to the binding and mobility of the water, and ultimately the potential for the hydrogel to dehydrate. As a preliminary study, in vitro evaporation rates were measured for a set of commercial contact lens hydrogels. Following this, comprehensive measurement of the temperature and water content dependencies of T1, T2 and D was performed for a series of commercial hydrogels that spanned the spectrum of equilibrium water content (EWC) and common compositions of contact lenses that are manufactured today. To quantify material differences, the data were then modelled based on theory that had been used for similar systems in the literature (Walker, Balmer et al., 1989, Hills, Takacs et al., 1989). The differences were related to differences in water binding and mobility. The evaporative results suggested that the EWC of the material was important in determining a material's potential to dehydrate in this way. Similarly, the NMR water self-diffusion coefficient was also found to be largely (if not wholly) determined by the WC. A specific binding model confirmed that the we was the dominant factor in determining the diffusive behaviour, but also suggested that subtle differences existed between the materials used, based on their equilibrium we (EWC). However, an alternative modified free volume model suggested that only the current water content of the material was important in determining the diffusive behaviour, and not the equilibrium water content. It was shown that T2 relaxation was dominated by chemical exchange between water and exchangeable polymer protons for materials that contained exchangeable polymer protons. The data was analysed using a proton exchange model, and the results were again reasonably correlated with EWC. Specifically, it was found that the average water mobility increased with increasing EWe approaching that of free water. The T1 relaxation was also shown to be reasonably well described by the same model. The main conclusion that can be drawn from this work is that the hydrogel EWe is an important parameter, which largely determines the behaviour of water in the gel. Higher EWe results in a hydrogel with water that behaves more like bulk water on average, or is less strongly 'bound' on average, compared with a lower EWe material. Based on the set of materials used, significant differences due to composition (for materials of the same or similar water content) could not be found. Similar studies could be used in the future to highlight hydrogels that deviate significantly from this 'average' behaviour, and may therefore have the least/greatest potential to dehydrate on the eye.

Swept frequency biompedance analysis for the determination of body water compartments

Bioelectrical impedance analysis, (BIA), is a method of body composition analysis first investigated in 1962 which has recently received much attention by a number of research groups. The reasons for this recent interest are its advantages, (viz: inexpensive, non-invasive and portable) and also the increasing interest in the diagnostic value of body composition analysis. The concept utilised by BIA to predict body water volumes is the proportional relationship for a simple cylindrical conductor, (volume oc length2/resistance), which allows the volume to be predicted from the measured resistance and length. Most of the research to date has measured the body's resistance to the passage of a 50· kHz AC current to predict total body water, (TBW). Several research groups have investigated the application of AC currents at lower frequencies, (eg 5 kHz), to predict extracellular water, (ECW). However all research to date using BIA to predict body water volumes has used the impedance measured at a discrete frequency or frequencies. This thesis investigates the variation of impedance and phase of biological systems over a range of frequencies and describes the development of a swept frequency bioimpedance meter which measures impedance and phase at 496 frequencies ranging from 4 kHz to 1 MHz. The impedance of any biological system varies with the frequency of the applied current. The graph of reactance vs resistance yields a circular arc with the resistance decreasing with increasing frequency and reactance increasing from zero to a maximum then decreasing to zero. Computer programs were written to analyse the measured impedance spectrum and determine the impedance, Zc, at the characteristic frequency, (the frequency at which the reactance is a maximum). The fitted locus of the measured data was extrapolated to determine the resistance, Ro, at zero frequency; a value that cannot be measured directly using surface electrodes. The explanation of the theoretical basis for selecting these impedance values (Zc and Ro), to predict TBW and ECW is presented. Studies were conducted on a group of normal healthy animals, (n=42), in which TBW and ECW were determined by the gold standard of isotope dilution. The prediction quotients L2/Zc and L2/Ro, (L=length), yielded standard errors of 4.2% and 3.2% respectively, and were found to be significantly better than previously reported, empirically determined prediction quotients derived from measurements at a single frequency. The prediction equations established in this group of normal healthy animals were applied to a group of animals with abnormally low fluid levels, (n=20), and also to a group with an abnormal balance of extra-cellular to intracellular fluids, (n=20). In both cases the equations using L2/Zc and L2/Ro accurately and precisely predicted TBW and ECW. This demonstrated that the technique developed using multiple frequency bioelectrical impedance analysis, (MFBIA), can accurately predict both TBW and ECW in both normal and abnormal animals, (with standard errors of the estimate of 6% and 3% for TBW and ECW respectively). Isotope dilution techniques were used to determine TBW and ECW in a group of 60 healthy human subjects, (male. and female, aged between 18 and 45). Whole body impedance measurements were recorded on each subject using the MFBIA technique and the correlations between body water volumes, (TBW and ECW), and heighe/impedance, (for all measured frequencies), were compared. The prediction quotients H2/Zc and H2/Ro, (H=height), again yielded the highest correlation with TBW and ECW respectively with corresponding standard errors of 5.2% and 10%. The values of the correlation coefficients obtained in this study were very similar to those recently reported by others. It was also observed that in healthy human subjects the impedance measured at virtually any frequency yielded correlations not significantly different from those obtained from the MFBIA quotients. This phenomenon has been reported by other research groups and emphasises the need to validate the technique by investigating its application in one or more groups with abnormalities in fluid levels. The clinical application of MFBIA was trialled and its capability of detecting lymphoedema, (an excess of extracellular fluid), was investigated. The MFBIA technique was demonstrated to be significantly more sensitive, (P<.05), in detecting lymphoedema than the current technique of circumferential measurements. MFBIA was also shown to provide valuable information describing the changes in the quantity of muscle mass of the patient during the course of the treatment. The determination of body composition, (viz TBW and ECW), by MFBIA has been shown to be a significant improvement on previous bioelectrical impedance techniques. The merit of the MFBIA technique is evidenced in its accurate, precise and valid application in animal groups with a wide variation in body fluid volumes and balances. The multiple frequency bioelectrical impedance analysis technique developed in this study provides accurate and precise estimates of body composition, (viz TBW and ECW), regardless of the individual's state of health.

Safety-restraint use rate as function of law enforcement and other factors : preliminary analysis

Persistent use of safety restraints prevents deaths and reduces the severity and number of injuries resulting from motor vehicle crashes. However, safety-restraint use rates in the United States have been below those of other nations with safety-restraint enforcement laws. With a better understanding of the relationship between safety-restraint law enforcement and safety-restraint use, programs can be implemented to decrease the number of deaths and injuries resulting from motor vehicle crashes. Does safety-restraint use increase as enforcement increases? Do motorists increase their safety-restraint use in response to the general presence of law enforcement or to targeted law enforcement efforts? Does a relationship between enforcement and restraint use exist at the countywide level? A logistic regression model was estimated by using county-level safety-restraint use data and traffic citation statistics collected in 13 counties within the state of Florida in 1997. The model results suggest that safety-restraint use is positively correlated with enforcement intensity, is negatively correlated with safety-restraint enforcement coverage (in lanemiles of enforcement coverage), and is greater in urban than rural areas. The quantification of these relationships may assist Florida and other law enforcement agencies in raising safety-restraint use rates by allocating limited funds more efficiently either by allocating additional time for enforcement activities of the existing force or by increasing enforcement staff. In addition, the research supports a commonsense notion that enforcement activities do result in behavioral response.

Digital constitutionalism and the role of the rule of law in the governance of virtual communities

This project proposes a new conceptual framework for the regulation of social networks and virtual communities. By applying a model based upon the rule of law, this thesis addresses the growing tensions that revolve around the public use of private networks. This research examines the shortcomings of traditional contractual governance models and cyberlaw theory and provides a reconstituted approach that will allow public constitutional-type interests to be recognised in the interpretation and enforcement of contractual doctrine.

Analysis of alternative water sources for use in the manufacture of concrete

In Australia and many other countries worldwide, water used in the manufacture of concrete must be potable. At present, it is currently thought that concrete properties are highly influenced by the water type used and its proportion in the concrete mix, but actually there is little knowledge of the effects of different, alternative water sources used in concrete mix design. Therefore, the identification of the level and nature of contamination in available water sources and their subsequent influence on concrete properties is becoming increasingly important. Of most interest, is the recycled washout water currently used by batch plants as mixing water for concrete. Recycled washout water is the water used onsite for a variety of purposes, including washing of truck agitator bowls, wetting down of aggregate and run off. This report presents current information on the quality of concrete mixing water in terms of mandatory limits and guidelines on impurities as well as investigating the impact of recycled washout water on concrete performance. It also explores new sources of recycled water in terms of their quality and suitability for use in concrete production. The complete recycling of washout water has been considered for use in concrete mixing plants because of the great benefit in terms of reducing the cost of waste disposal cost and environmental conservation. The objective of this study was to investigate the effects of using washout water on the properties of fresh and hardened concrete. This was carried out by utilizing a 10 week sampling program from three representative sites across South East Queensland. The sample sites chosen represented a cross-section of plant recycling methods, from most effective to least effective. The washout water samples collected from each site were then analysed in accordance with Standards Association of Australia AS/NZS 5667.1 :1998. These tests revealed that, compared with tap water, the washout water was higher in alkalinity, pH, and total dissolved solids content. However, washout water with a total dissolved solids content of less than 6% could be used in the production of concrete with acceptable strength and durability. These results were then interpreted using chemometric techniques of Principal Component Analysis, SIMCA and the Multi-Criteria Decision Making methods PROMETHEE and GAIA were used to rank the samples from cleanest to unclean. It was found that even the simplest purifying processes provided water suitable for the manufacture of concrete form wash out water. These results were compared to a series of alternative water sources. The water sources included treated effluent, sea water and dam water and were subject to the same testing parameters as the reference set. Analysis of these results also found that despite having higher levels of both organic and inorganic properties, the waters complied with the parameter thresholds given in the American Standard Test Method (ASTM) C913-08. All of the alternative sources were found to be suitable sources of water for the manufacture of plain concrete.

Diffusion tensor of water in model articular cartilage

We used Monte Carlo simulations of Brownian dynamics of water to study anisotropic water diffusion in an idealised model of articular cartilage. The main aim was to use the simulations as a tool for translation of the fractional anisotropy of the water diffusion tensor in cartilage into quantitative characteristics of its collagen fibre network. The key finding was a linear empirical relationship between the collagen volume fraction and the fractional anisotropy of the diffusion tensor. Fractional anisotropy of the diffusion tensor is potentially a robust indicator of the microstructure of the tissue because, in the first approximation, it is invariant to the inclusion of proteoglycans or chemical exchange between free and collagen-bound water in the model. We discuss potential applications of Monte Carlo diffusion-tensor simulations for quantitative biophysical interpretation of MRI diffusion-tensor images of cartilage. Extension of the model to include collagen fibre disorder is also discussed.

The Conceptual Basis of Personal Information in Australian Privacy Law

Australian privacy law regulates how government agencies and private sector organisations collect, store and use personal information. A coherent conceptual basis of personal information is an integral requirement of information privacy law as it determines what information is regulated. A 2004 report conducted on behalf of the UK’s Information Commissioner (the 'Booth Report') concluded that there was no coherent definition of personal information currently in operation because different data protection authorities throughout the world conceived the concept of personal information in different ways. The authors adopt the models developed by the Booth Report to examine the conceptual basis of statutory definitions of personal information in Australian privacy laws. Research findings indicate that the definition of personal information is not construed uniformly in Australian privacy laws and that different definitions rely upon different classifications of personal information. A similar situation is evident in a review of relevant case law. Despite this, the authors conclude the article by asserting that a greater jurisprudential discourse is required based on a coherent conceptual framework to ensure the consistent development of Australian privacy law.

Systematic variations in polymer gel dosimeter calibration due to container influence and deviations from water equivalence

There are a number of gel dosimeter calibration methods in contemporary usage. The present study is a detailed Monte Carlo investigation into the accuracy of several calibration techniques. Results show that for most arrangements the dose to gel accurately reflects the dose to water, with the most accurate method involving the use of a large diameter flask of gel into which multiple small fields of varying dose are directed. The least accurate method was found to be that of a long test tube in a water phantom, coaxial with the beam. The large flask method is also the most straightforward and least likely to introduce errors during setup, though, to its detriment, the volume of gel required is much more than other methods.

A comparative study of the effect of calibration conditions on the water equivalence of a range of gel dosimeters

Gel dosimeters are of increasing interest in the field of radiation oncology as the only truly three-dimensional integrating radiation dosimeter. There are a range of ferrous-sulphate and polymer gel dosimeters. To be of use, they must be water-equivalent. On their own, this relates to their radiological properties as determined by their composition. In the context of calibration of gel dosimeters, there is the added complexity of the calibration geometry; the presence of containment vessels may influence the dose absorbed. Five such methods of calibration are modelled here using the Monte Carlo method. It is found that the Fricke gel best matches water for most of the calibration methods, and that the best calibration method involves the use of a large tub into which multiple fields of different dose are directed. The least accurate calibration method involves the use of a long test tube along which a depth dose curve yields multiple calibration points.

A comparative study of the effect of calibration conditions on the water equivalence of a range of gel dosimeters

Gel dosimeters are of increasing interest in the field of radiation oncology as the only truly three-dimensional integrating radiation dosimeter. There are a range of ferrous-sulphate and polymer gel dosimeters. To be of use, they must be water-equivalent. On their own, this relates to their radiological properties as determined by their composition. In the context of calibration of gel dosimeters, there is the added complexity of the calibration geometry; the presence of containment vessels may influence the dose absorbed. Five such methods of calibration are modelled here using the Monte Carlo method. It is found that the Fricke gel best matches water for most of the calibration methods, and that the best calibration method involves the use of a large tub into which multiple fields of different dose are directed. The least accurate calibration method involves the use of a long test tube along which a depth dose curve yields multiple calibration points.

The relationship of boat movements to environmental management at some Queensland marinas

Marinas currently exist primarily to service recreational boats, and these vessels are a potential cause of both problems and opportunities in environmental management. Thus, on the one hand, destructive fuel and other pollutants may be expelled, boat wakes can cause littoral soil erosion, physical damage results from collisions with marine life, and litter and noise pollution occur in otherwise pristine habitat. Boats also provide access to otherwise inaccessible natural environments for educational and other management reasons. In this study, boat traffic at three large marinas located along the Queensland coastline has been field surveyed for introductory information. No attempt was made at this juncture to survey the behaviour of the boat crews and passengers (concerning actual destinations, activities on board, etc. or to survey the recreational boat industry. Such studies rely on boat registration records and personal questionnaires. Some other surveys relating to fishing draw on boat ramp surveys and direct submissions by recreational fishers; these provide some data on daily usage of boat ramps, but without particular attention to boats. We believe field observations of overall boat activities in the water are necessary for environmental management purposes. The aim of the survey was to provide information to help prioritize the potential impacts that boats’ activities have on the surrounding natural environment. Any impact by boats will be a product of their numbers, size, frequency of movement, carrying capacity and routes/destinations. The severity of impacts will dictate the appropriate management action.