Influences of biodiesel chemical compositions and physical properties on engine exhaust particle emissions

This thesis presents a comprehensive study on the influences of biodiesel chemical composition and physical properties on diesel engine exhaust particle emissions. It examines biodiesels from several feedstocks having wide variations in their chemical composition (carbon chain length, unsaturation and oxygen content) and physical properties (density, viscosity, surface tension, boiling point etc.), and evaluates their influence on exhaust particle emissions. The outcome of this thesis is significant since it reveals the importance of regulating biodiesels chemical composition in order to ensure lowest possible emissions with better overall performance.

Restraint in the age of speed: Protecting vulnerable news sources in the 24/7 global news cycle

As news communication speeds up, investigative journalists have an increasing responsibility to minimise the risk of harm to vulnerable news sources. In addition, the increased longevity and instant global search-ability of news coverage and investigative journalism outputs such as documentaries, places upon journalists an increased responsibility for accuracy since online coverage cannot be easily corrected or retracted. This paper will examine how the risks to a news source and her family were considered and mitigated during the production of a radio documentary and newspaper story about an intended victim of child sacrifice. Pre-publication considerations included the possible risks to the mental health of the news source, the potential physical risk to her children and the risk to future family relationships. To hear the ABC Radio National documentary, A living sacrifice, on 360 Documentaries prior to the conference, see http://www.abc.net.au/radionational/programs/360/a-living-sacrifice/5359744. To read the Sunday Mail newspaper coverage of the story see http://www.couriermail.com.au/news/queensland/susannah-birch-talks-about-her-throat-being-slit-by-her-mother-when-she-was-a-baby/story-fnihsrf2-1226881911465.

Acute restraint stress alters subsequent auditory fear conditioning in the rat

The neural basis of Pavlovian fear conditioning is well understood and depends upon neural processes within the amygdala. Stress is known to play a role in the modulation of fear-related behavior, including Pavlovian fear conditioning. Chronic restraint stress has been shown to enhance fear conditioning to discrete and contextual stimuli; however, the time course and extent of restraint that is essential for this modulation of fear learning remains unclear. Thus, we tested the extent to which a single exposure to 1 hr of restraint would alter subsequent auditory fear conditioning in rats.

Can perceptual indices estimate physiological strain across a range of environments and metabolic workloads when wearing explosive ordnance disposal and chemical protective clothing?

Objective Explosive ordnance disposal (EOD) often requires technicians to wear multiple protective garments in challenging environmental conditions. The accumulative effect of increased metabolic cost coupled with decreased heat dissipation associated with these garments predisposes technicians to high levels of physiological strain. It has been proposed that a perceptual strain index (PeSI) using subjective ratings of thermal sensation and perceived exertion as surrogate measures of core body temperature and heart rate, may provide an accurate estimation of physiological strain. Therefore, this study aimed to determine if the PeSI could estimate the physiological strain index (PSI) across a range of metabolic workloads and environments while wearing heavy EOD and chemical protective clothing. Methods Eleven healthy males wore an EOD and chemical protective ensemble while walking on a treadmill at 2.5, 4 and 5.5 km·h− 1 at 1% grade in environmental conditions equivalent to wet bulb globe temperature (WBGT) 21, 30 and 37 °C. WBGT conditions were randomly presented and a maximum of three randomised treadmill walking trials were completed in a single testing day. Trials were ceased at a maximum of 60-min or until the attainment of termination criteria. A Pearson's correlation coefficient, mixed linear model, absolute agreement and receiver operating characteristic (ROC) curves were used to determine the relationship between the PeSI and PSI. Results A significant moderate relationship between the PeSI and the PSI was observed [r = 0.77; p < 0.001; mean difference = 0.8 ± 1.1 a.u. (modified 95% limits of agreement − 1.3 to 3.0)]. The ROC curves indicated that the PeSI had a good predictive power when used with two, single-threshold cut-offs to differentiate between low and high levels of physiological strain (area under curve: PSI three cut-off = 0.936 and seven cut-off = 0.841). Conclusions These findings support the use of the PeSI for monitoring physiological strain while wearing EOD and chemical protective clothing. However, future research is needed to confirm the validity of the PeSI for active EOD technicians operating in the field.

Evaluation of a meteorological and three-dimensional chemical transport model for gaseous and particle concentrations in an urban airshed

The Air Pollution Model and Chemical Transport Model (TAPM-CTM) framework has been tested and applied originally in Sydney to quantify particle and gaseous concentration (Cope et al, 2014). However, the model performance had not been tested in the south-eastern Queensland region (SEQR), Australia.

Designing and evaluating a persuasive child restraint television commercial

Objective Relatively high rates of child restraint inappropriate use, misuse and faults in the installation of restraints have suggested a crucial need for public education messages to raise parental awareness of the need to use restraints correctly. This project involved the devising and pilot testing of message concepts, filming of a television advertisement (the TVC), and the evaluation of the TVC. This paper focuses specifically upon the evaluation of the TVC. The development and evaluation of the TVC were guided by an extended Theory of Planned Behaviour which comprised the standard constructs of attitude, subjective norm, and perceived behavioural control as well as the additional constructs of group norm and descriptive norm. The study also explored the extent to which parents with low and high intentions to self-check restraint/s differed on salient beliefs regarding the behaviour. Methods An online survey of parents (N = 384) was conducted where parents were randomly assigned to either an Intervention group (n = 161), and therefore viewed the advertisement within the survey, or the Control group (n = 223) and therefore did not view the advertisement. Results Following a one-off exposure to the TVC, the results indicated that, although not a significant difference, parents in the Intervention group reported stronger intentions (M = 4.43, SD = .74) to self-check restraints than parents in the Control group (M = 4.18, SD = .86). Also, parents in the Intervention group (M = 4.59, SD = .47) reported significantly higher levels of perceived behavioural control than parents in the Control group (M = 4.40, SD = .73). The regression results revealed that, for parents in the Intervention group, attitude and group norm were significant predictors of parental intentions to self-check their child restraint. Finally, the exploratory analyses of parental beliefs suggested that those parents with low intentions to self-check child restraints were significantly more likely than high intenders to agree that they did not have enough time to check restraints or that having a child in a restraint is more important than checking the installation of the restraint. Conclusion Overall, the findings provide some support for the persuasiveness of the child restraint TVC and provide insight into the factors influencing reported parental intentions as well as salient beliefs underpinning self-checking of restraints. Interventions that attempt to increase parental perceptions of the importance of self-checking restraints regularly and brevity of the time involved in doing so may be effective.

Effects of biodiesel chemical composition on the chemical and physical properties of the primary and secondary diesel particulate matter

This thesis improves our insight towards the effects of using biodiesels on the particulate matter emission of diesel engines and contributes to our understanding of their potential adverse health effects. The novelty of this project is the use of biodiesel fuel with controlled chemical composition that enables us to relate changes of physiochemical properties of particles to specific properties of the biodiesel. For the first time, the possibility of a correlation of the volatility and the Reactive Oxygen Species concentration of the particles is investigated versus the saturation, oxygen content and carbon chain length of the fuel.

Fast growth of polycrystalline graphene by chemical vapor deposition of ethanol on copper

High conductive graphene films can be grown on metal foils by chemical vapor deposition (CVD). We here analyzed the use of ethanol, an economic precursor, which results also safer than commonly-used methane. A comprehensive range of process parameters were explored in order to obtain graphene films with optimal characteristics in view of their use in optoelectronics and photovoltaics. Commercially-available and electro-polished copper foils were used as substrates. By finely tuning the CVD conditions, we obtained few-layer (2-4) graphene films with good conductivity (-500 Ohm/sq) and optical transmittance around 92-94% at 550 nm on unpolished copper foils. The growth on electro-polished copper provides instead predominantly mono-layer films with lower conductivity (>1000 Ohm/sq) and with a transmittance of 97.4% at 550 nm. As for the device properties, graphene with optimal properties as transparent conductive film were produced by CVD on standard copper with specific process conditions.

Stochastic linear multistep methods for the simulation of chemical kinetics

In this paper, we introduce the Stochastic Adams-Bashforth (SAB) and Stochastic Adams-Moulton (SAM) methods as an extension of the tau-leaping framework to past information. Using the theta-trapezoidal tau-leap method of weak order two as a starting procedure, we show that the k-step SAB method with k >= 3 is order three in the mean and correlation, while a predictor-corrector implementation of the SAM method is weak order three in the mean but only order one in the correlation. These convergence results have been derived analytically for linear problems and successfully tested numerically for both linear and non-linear systems. A series of additional examples have been implemented in order to demonstrate the efficacy of this approach.

The doctrine of necessity and the detention and restraint of people with intellectual impairment: Is there any justification?

In Australia, the legal basis for the detention and restraint of people with intellectual impairment is ad hoc and unclear. There is no comprehensive legal framework that authorises and regulates the detention of, for example, older people with dementia in locked wards or in residential aged care, people with disability in residential services or people with acquired brain injury in hospital and rehabilitation services. This paper focuses on whether the common law doctrine of necessity (or its statutory equivalents) should have a role in permitting the detention and restraint of people with disabilities. Traditionally, the defence of necessity has been recognised as an excuse, where the defendant, faced by a situation of imminent peril, is excused from the criminal or civil liability because of the extraordinary circumstances they find themselves in. In the United Kingdom, however, in In re F (Mental Patient: Sterilisation) and R v Bournewood Community and Mental Health NHS Trust, ex parte L, the House of Lords broadened the defence so that it operated as a justification for treatment, detention and restraint outside of the emergency context. This paper outlines the distinction between necessity as an excuse and as a defence, and identifies a number of concerns with the latter formulation: problems of democracy, integrity, obedience, objectivity and safeguards. Australian courts are urged to reject the United Kingdom approach and retain an excuse-based defence, as the risks of permitting the essentially utilitarian model of necessity as a justification are too great.

Double diffusive Marangoni convection flow of electrically conducting fluid in a square cavity with chemical reaction

Double diffusive Marangoni convection flow of viscous incompressible electrically conducting fluid in a square cavity is studied in this paper by taking into consideration of the effect of applied magnetic field in arbitrary direction and the chemical reaction. The governing equations are solved numerically by using alternate direct implicit (ADI) method together with the successive over relaxation (SOR) technique. The flow pattern with the effect of governing parameters, namely the buoyancy ratio W, diffusocapillary ratio w, and the Hartmann number Ha, is investigated. It is revealed from the numerical simulations that the average Nusselt number decreases; whereas the average Sherwood number increases as the orientation of magnetic field is shifted from horizontal to vertical. Moreover, the effect of buoyancy due to species concentration on the flow is stronger than the one due to thermal buoyancy. The increase in diffusocapillary parameter, w caus

Efficient simulation of stochastic chemical kinetics with the Stochastic Bulirsch-Stoer extrapolation method

Background Biochemical systems with relatively low numbers of components must be simulated stochastically in order to capture their inherent noise. Although there has recently been considerable work on discrete stochastic solvers, there is still a need for numerical methods that are both fast and accurate. The Bulirsch-Stoer method is an established method for solving ordinary differential equations that possesses both of these qualities. Results In this paper, we present the Stochastic Bulirsch-Stoer method, a new numerical method for simulating discrete chemical reaction systems, inspired by its deterministic counterpart. It is able to achieve an excellent efficiency due to the fact that it is based on an approach with high deterministic order, allowing for larger stepsizes and leading to fast simulations. We compare it to the Euler τ-leap, as well as two more recent τ-leap methods, on a number of example problems, and find that as well as being very accurate, our method is the most robust, in terms of efficiency, of all the methods considered in this paper. The problems it is most suited for are those with increased populations that would be too slow to simulate using Gillespie’s stochastic simulation algorithm. For such problems, it is likely to achieve higher weak order in the moments. Conclusions The Stochastic Bulirsch-Stoer method is a novel stochastic solver that can be used for fast and accurate simulations. Crucially, compared to other similar methods, it better retains its high accuracy when the timesteps are increased. Thus the Stochastic Bulirsch-Stoer method is both computationally efficient and robust. These are key properties for any stochastic numerical method, as they must typically run many thousands of simulations.

A novel near-infrared spectroscopy and chemometrics method for rapid analysis of several chemical components and antioxidant activity of mint (mentha haplocalyx briq.) samples

A novel near-infrared spectroscopy (NIRS) method has been researched and developed for the simultaneous analyses of the chemical components and associated properties of mint (Mentha haplocalyx Briq.) tea samples. The common analytes were: total polysaccharide content, total flavonoid content, total phenolic content, and total antioxidant activity. To resolve the NIRS data matrix for such analyses, least squares support vector machines was found to be the best chemometrics method for prediction, although it was closely followed by the radial basis function/partial least squares model. Interestingly, the commonly used partial least squares was unsatisfactory in this case. Additionally, principal component analysis and hierarchical cluster analysis were able to distinguish the mint samples according to their four geographical provinces of origin, and this was further facilitated with the use of the chemometrics classification methods-K-nearest neighbors, linear discriminant analysis, and partial least squares discriminant analysis. In general, given the potential savings with sampling and analysis time as well as with the costs of special analytical reagents required for the standard individual methods, NIRS offered a very attractive alternative for the simultaneous analysis of mint samples.

Particle emissions from biodiesels with different physical properties and chemical composition

Biodiesels produced from different feedstocks usually have wide variations in their fatty acid methyl ester (FAME) so that their physical properties and chemical composition are also different. The aim of this study is to investigate the effect of the physical properties and chemical composition of biodiesels on engine exhaust particle emissions. Alongside with neat diesel, four biodiesels with variations in carbon chain length and degree of unsaturation have been used at three blending ratios (B100, B50, B20) in a common rail engine. It is found that particle emission increased with the increase of carbon chain length. However, for similar carbon chain length, particle emissions from biodiesel having relatively high average unsaturation are found to be slightly less than that of low average unsaturation. Particle size is also found to be dependent on fuel type. The fuel or fuel mix responsible for higher particle mass (PM) and particle number (PN) emissions is also found responsible for larger particle median size. Particle emissions reduced consistently with fuel oxygen content regardless of the proportion of biodiesel in the blends, whereas it increased with fuel viscosity and surface tension only for higher diesel–biodiesel blend percentages (B100, B50). However, since fuel oxygen content increases with the decreasing carbon chain length, it is not clear which of these factors drives the lower particle emission. Overall, it is evident from the results presented here that chemical composition of biodiesel is more important than its physical properties in controlling exhaust particle emissions.

Systematic and Day-to-Day Effects of Chemical-Derived Population Estimates on Wastewater-Based Drug Epidemiology

Population size is crucial when estimating population-normalized drug consumption (PNDC) from wastewater-based drug epidemiology (WBDE). Three conceptually different population estimates can be used: de jure (common census, residence), de facto (all persons within a sewer catchment), and chemical loads (contributors to the sampled wastewater). De facto and chemical loads will be the same where all households contribute to a central sewer system without wastewater loss. This study explored the feasibility of determining a de facto population and its effect on estimating PNDC in an urban community over an extended period. Drugs and other chemicals were analyzed in 311 daily composite wastewater samples. The daily estimated de facto population (using chemical loads) was on average 32% higher than the de jure population. Consequently, using the latter would systemically overestimate PNDC by 22%. However, the relative day-to-day pattern of drug consumption was similar regardless of the type of normalization as daily illicit drug loads appeared to vary substantially more than the population. Using chemical loads population, we objectively quantified the total methodological uncertainty of PNDC and reduced it by a factor of 2. Our study illustrated the potential benefits of using chemical loads population for obtaining more robust PNDC data in WBDE.