Intrinsic kinetics of titania photocatalysis : simplified models for their investigation

Even though titanium dioxide photocatalysis has been promoted as a leading green technology for water purification, many issues have hindered its application on a large commercial scale. For the materials scientist the main issues have centred the synthesis of more efficient materials and the investigation of degradation mechanisms; whereas for the engineers the main issues have been the development of appropriate models and the evaluation of intrinsic kinetics parameters that allow the scale up or re-design of efficient large-scale photocatalytic reactors. In order to obtain intrinsic kinetics parameters the reaction must be analysed and modelled considering the influence of the radiation field, pollutant concentrations and fluid dynamics. In this way, the obtained kinetic parameters are independent of the reactor size and configuration and can be subsequently used for scale-up purposes or for the development of entirely new reactor designs. This work investigates the intrinsic kinetics of phenol degradation over titania film due to the practicality of a fixed film configuration over a slurry. A flat plate reactor was designed in order to be able to control reaction parameters that include the UV irradiance, flow rates, pollutant concentration and temperature. Particular attention was paid to the investigation of the radiation field over the reactive surface and to the issue of mass transfer limited reactions. The ability of different emission models to describe the radiation field was investigated and compared to actinometric measurements. The RAD-LSI model was found to give the best predictions over the conditions tested. Mass transfer issues often limit fixed film reactors. The influence of this phenomenon was investigated with specifically planned sets of benzoic acid experiments and with the adoption of the stagnant film model. The phenol mass transfer coefficient in the system was calculated to be km,phenol=8.5815x10-7Re0.65(ms-1). The data obtained from a wide range of experimental conditions, together with an appropriate model of the system, has enabled determination of intrinsic kinetic parameters. The experiments were performed in four different irradiation levels (70.7, 57.9, 37.1 and 20.4 W m-2) and combined with three different initial phenol concentrations (20, 40 and 80 ppm) to give a wide range of final pollutant conversions (from 22% to 85%). The simple model adopted was able to fit the wide range of conditions with only four kinetic parameters; two reaction rate constants (one for phenol and one for the family of intermediates) and their corresponding adsorption constants. The intrinsic kinetic parameters values were defined as kph = 0.5226 mmol m-1 s-1 W-1, kI = 0.120 mmol m-1 s-1 W-1, Kph = 8.5 x 10-4 m3 mmol-1 and KI = 2.2 x 10-3 m3 mmol-1. The flat plate reactor allowed the investigation of the reaction under two different light configurations; liquid and substrate side illumination. The latter of particular interest for real world applications where light absorption due to turbidity and pollutants contained in the water stream to be treated could represent a significant issue. The two light configurations allowed the investigation of the effects of film thickness and the determination of the catalyst optimal thickness. The experimental investigation confirmed the predictions of a porous medium model developed to investigate the influence of diffusion, advection and photocatalytic phenomena inside the porous titania film, with the optimal thickness value individuated at 5 ìm. The model used the intrinsic kinetic parameters obtained from the flat plate reactor to predict the influence of thickness and transport phenomena on the final observed phenol conversion without using any correction factor; the excellent match between predictions and experimental results provided further proof of the quality of the parameters obtained with the proposed method.

Inactivation and structural changes of E. Cloacae and B. Subtilis Endospores during IR laser water treatment

IR radiation has been studied for micro-organism inactivation of bacterial spores on metal substrates [1] and on metal and paper substrates [2]. A near-point near infrared laser water treatment apparatus for use in dental hand-pieces was also developed [3]. To date water sterilisation research using a mid-IR laser technique is very rare. According to the World Health Organisation [4], examinations for faecal indicator bacteria remain the most sensitive and specific way of assessing the hygienic quality of water. Bacteria that fall into this group are E. coli, other coliform bacteria (including E. cloacae) and to a lesser extent, faecal streptococci [5]. Protozoan cysts from organisms which cause giardiasis are the most frequently identified cause of waterborne diseases in developed countries [6,7]. The use of aerobic bacterial endospores to monitor the efficiency of various water treatments has been shown to provide a reliable and simple indicator of overall performance of water treatment[8,9].The efficacy of IR radiation for water disinfection compared to UV treatment has been further investigated in the present study. In addition FTIR spectroscopy in conjunction with Principle Component Analysis was used to characterise structural changes within the bacterial cells and endospores following IR laser treatment. Changes in carbohydrate content of E. cloacae following IR laser treatment were observed.

Molecular characterisation of environmental enterococci derived from water samples and assessment of associated public health hazards

Enterococci are versatile Gram-positive bacteria that can survive under extreme conditions. Most enterococci are non-virulent and found in the gastrointestinal tract of humans and animals. Other strains are opportunistic pathogens that contribute to a large number of nosocomial infections globally. Epidemiological studies demonstrated a direct relationship between the density of enterococci in surface waters and the risk of swimmer-associated gastroenteritis. The distribution of infectious enterococcal strains from the hospital environment or other sources to environmental water bodies through sewage discharge or other means, could increase the prevalence of these strains in the human population. Environmental water quality studies may benefit from focusing on a subset of Enterococcus spp. that are consistently associated with sources of faecal pollution such as domestic sewage, rather than testing for the entire genus. E. faecalis and E. faecium are potentially good focal species for such studies, as they have been consistently identified as the dominant Enterococcus spp. in human faeces and sewage. On the other hand enterococcal infections are predominantly caused by E. faecalis and E. faecium. The characterisation of E. faecalis and E. faecium is important in studying their population structures, particularly in environmental samples. In developing and implementing rapid, robust molecular genotyping techniques, it is possible to more accurately establish the relationship between human and environmental enterococci. Of particular importance, is to determine the distribution of high risk enterococcal clonal complexes, such as E. faecium clonal complex 17 and E. faecalis clonal complexes 2 and 9 in recreational waters. These clonal complexes are recognized as particularly pathogenic enterococcal genotypes that cause severe disease in humans globally. The Pimpama-Coomera watershed is located in South East Queensland, Australia and was investigated in this study mainly because it is used intensively for agriculture and recreational purposes and has a strong anthropogenic impact. The primary aim of this study was to develop novel, universally applicable, robust, rapid and cost effective genotyping methods which are likely to yield more definitive results for the routine monitoring of E. faecalis and E. faecium, particularly in environmental water sources. To fullfill this aim, new genotyping methods were developed based on the interrogation of highly informative single nucleotide polymorphisms (SNPs) located in housekeeping genes of both E. faecalis and E. faecium. SNP genotyping was successfully applied in field investigations of the Coomera watershed, South-East Queensland, Australia. E. faecalis and E. faecium isolates were grouped into 29 and 23 SNP profiles respectively. This study showed the high longitudinal diversity of E. faecalis and E. faecium over a period of two years, and both human-related and human-specific SNP profiles were identified. Furthermore, 4.25% of E. faecium strains isolated from water was found to correspond to the important clonal complex-17 (CC17). Strains that belong to CC17 cause the majority of hospital outbreaks and clinical infections globally. Of the six sampling sites of the Coomera River, Paradise Point had the highest number of human-related and human-specific E. faecalis and E. faecium SNP profiles. The secondary aim of this study was to determine the antibiotic-resistance profiles and virulence traits associated with environmental E. faecalis and E. faecium isolates compared to human pathogenic E. faecalis and E. faecium isolates. This was performed to predict the potential health risks associated with coming into contact with these strains in the Coomera watershed. In general, clinical isolates were found to be more resistant to all the antibiotics tested compared to water isolates and they harbored more virulence traits. Multi-drug resistance was more prevalent in clinical isolates (71.18% of E. faecalis and 70.3 % of E. faecium) compared to water isolates (only 5.66 % E. faecium). However, tetracycline, gentamicin, ciprofloxacin and ampicillin resistance was observed in water isolates. The virulence gene esp was the most prevalent virulence determinant observed in clinical isolates (67.79% of E. faecalis and 70.37 % of E. faecium), and this gene has been described as a human-specific marker used for microbial source tracking (MST). The presence of esp in water isolates (16.36% of E. faecalis and 19.14% of E. faecium) could be indicative of human faecal contamination in these waterways. Finally, in order to compare overall gene expression between environmental and clinical strains of E. faecalis, a comparative gene hybridization study was performed. The results of this investigation clearly demonstrated the up-regulation of genes associated with pathogenicity in E. faecalis isolated from water. The expression study was performed at physiological temperatures relative to ambient temperatures. The up-regulation of virulence genes demonstrates that environmental strains of E. faecalis can pose an increased health risk which can lead to serious disease, particularly if these strains belong to the virulent CC17 group. The genotyping techniques developed in this study not only provide a rapid, robust and highly discriminatory tool to characterize E. faecalis and E. faecium, but also enables the efficient identification of virulent enterococci that are distributed in environmental water sources.

Relating vehicle generated pollutants to urban stormwater quality

Rapid urbanisation and resulting continuous increase in traffic has been recognised as key factors in the contribution of increased pollutant loads to urban stormwater and in turn to receiving waters. Urbanisation primarily increases anthropogenic activities and the percentage of impervious surfaces in urban areas. These processes are collectively responsible for urban stormwater pollution. In this regard, urban traffic and land use related activities have been recognised as the primary pollutant sources. This is primarily due to the generation of a range of key pollutants such as solids, heavy metals and PAHs. Appropriate treatment system design is the most viable approach to mitigate stormwater pollution. However, limited understanding of the pollutant process and transport pathways constrains effective treatment design. This highlights necessity for the detailed understanding of traffic and other land use related pollutants processes and pathways in relation to urban stormwater pollution. This study has created new knowledge in relation to pollutant processes and transport pathways encompassing atmospheric pollutants, atmospheric deposition and build-up on ground surfaces of traffic generated key pollutants. The research study was primarily based on in-depth experimental investigations. This thesis describes the extensive knowledge created relating to the processes of atmospheric pollutant build-up, atmospheric deposition and road surface build-up and establishing their relationships as a chain of processes. The analysis of atmospheric deposition revealed that both traffic and land use related sources contribute total suspended particulate matter (TSP) to the atmosphere. Traffic sources become dominant during weekdays whereas land use related sources become dominant during weekends due to the reduction in traffic sources. The analysis further concluded that atmospheric TSP, polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) concentrations are highly influenced by total average daily heavy duty traffic, traffic congestion and the fraction of commercial and industrial land uses. A set of mathematical equation were developed to predict TSP, PAHs and HMs concentrations in the atmosphere based on the influential traffic and land use related parameters. Dry deposition samples were collected for different antecedent dry days and wet deposition samples were collected immediately after rainfall events. The dry deposition was found to increase with the antecedent dry days and consisted of relatively coarser particles (greater than 1.4 ìm) when compared to wet deposition. The wet deposition showed a strong affinity to rainfall depth, but was not related to the antecedent dry period. It was also found that smaller size particles (less than 1.4 ìm) travel much longer distances from the source and deposit mainly with the wet deposition. Pollutants in wet deposition are less sensitive to the source characteristics compared to dry deposition. Atmospheric deposition of HMs is not directly influenced by land use but rather by proximity to high emission sources such as highways. Therefore, it is important to consider atmospheric deposition as a key pollutant source to urban stormwater in the vicinity of these types of sources. Build-up was analysed for five different particle size fractions, namely, <1 ìm, 1-75 ìm, 75-150 ìm, 150-300 ìm and >300 ìm for solids, PAHs and HMs. The outcomes of the study indicated that PAHs and HMs in the <75 ìm size fraction are generated mainly by traffic related activities whereas the > 150 ìm size fraction is generated by both traffic and land use related sources. Atmospheric deposition is an important source for HMs build-up on roads, whereas the contribution of PAHs from atmospheric sources is limited. A comprehensive approach was developed to predict traffic and other land use related pollutants in urban stormwater based on traffic and other land use characteristics. This approach primarily included the development of a set of mathematical equations to predict traffic generated pollutants by linking traffic and land use characteristics to stormwater quality through mathematical modelling. The outcomes of this research will contribute to the design of appropriate treatment systems to safeguard urban receiving water quality for future traffic growth scenarios. The „real world. application of knowledge generated was demonstrated through mathematical modelling of solids in urban stormwater, accounting for the variability in traffic and land use characteristics.

Impact of roof surface runoff on urban water quality

The pollutant impacts of urban stormwater runoff on receiving waters are well documented in research literature. However, it is road surfaces that are commonly identified as the significant pollutant source. This paper presents the outcomes of an extensive program of research into the role of roof surfaces in urban water quality with particular focus on solids, nutrients and organic carbon. The outcomes confirmed that roof surfaces play an important role in influencing the pollutant characteristics of urban stormwater runoff. Pollutant build-up and wash-off characteristics for roads and roof surfaces were found to be appreciably different. The pollutant wash-off characteristics exhibited by roof surfaces show that it influences the first flush phenomenon more significantly than road surfaces. In most urban catchments, as roof surfaces constitutes a higher fraction of impervious area compared to road surfaces, it is important that the pollutant generation role of roof surfaces is specifically taken into consideration in stormwater quality mitigation strategies.

Modelling resilience in a water supply system : contrasting conditions of drought and flood

This paper presents an approach to modelling the resilience of a generic (potable) water supply system. The system is contextualized as a meta-system consisting of three subsystems to represent the natural catchment, the water treatment plant and the water distribution infrastructure for urban use. An abstract mathematical model of the meta-system is disaggregated progressively to form a cascade of equations forming a relational matrix of models. This allows the investigation of commonly implicit relationships between various operational components within the meta system, the in-depth understanding of specific system components and influential factors and the incorporation of explicit disturbances to explore system behaviour. Consequently, this will facilitate long-term decision making to achieve sustainable solutions for issues such as, meeting a growing demand or managing supply-side influences in the meta-system under diverse water availability regimes. This approach is based on the hypothesis that the means to achieve resilient supply of water may be better managed by modelling the effects of changes at specific levels that have a direct or in some cases indirect impact on higher-order outcomes. Additionally, the proposed strategy allows the definition of approaches to combine disparate data sets to synthesise previously missing or incomplete higher-order information, a scientifically robust means to define and carry out meta-analyses using knowledge from diverse yet relatable disciplines relevant to different levels of the system and for enhancing the understanding of dependencies and inter-dependencies of variable factors at various levels across the meta-system. The proposed concept introduces an approach for modelling a complex infrastructure system as a meta system which consists of a combination of bio-ecological, technical and socio-technical subsystems.

Sustainable education buildings in Australia : a green star review

In order to promote green building practice in Australia, the Green Building Council of Australia (GBCA) launched the Green Star rating tools for various types of buildings built since 2003. Of these, the Green Star-Education rating tool addresses sustainability issues during the design and construction phrases of education facility development. It covers a number of categories, including Management, Indoor Environment Quality, Energy, Transport, Water, Materials, Land Use & Ecology, Emissions and Innovation. This paper reviews the use of the Green Star system in Australian education facilities construction and the potential challenges associated with Green Star- Education implementation. Score sheets of 34 education projects across Australia that achieved Green Star certification were collected and analysed. The percentage of green star points obtained within each category and sub-category (credits) for each project were analysed to illustrate the achievement of credits. The results show that management-related credits and ecology-related credits are the easiest and most difficult to obtain respectively. The study also indicted that 6 Green Star education projects obtained particularly high percentages in the Innovation category. The investigation of points obtained in each category provides prospective Green Star applicants with insights into credit achievement for future projects.