A catchment modelling approach integrating surface and groundwater processes, land use and distribution of nutrients : Elimbah Creek, southeast Queensland

As the world’s population is growing, so is the demand for agricultural products. However, natural nitrogen (N) fixation and phosphorus (P) availability cannot sustain the rising agricultural production, thus, the application of N and P fertilisers as additional nutrient sources is common. It is those anthropogenic activities that can contribute high amounts of organic and inorganic nutrients to both surface and groundwaters resulting in degradation of water quality and a possible reduction of aquatic life. In addition, runoff and sewage from urban and residential areas can contain high amounts of inorganic and organic nutrients which may also affect water quality. For example, blooms of the cyanobacterium Lyngbya majuscula along the coastline of southeast Queensland are an indicator of at least short term decreases of water quality. Although Australian catchments, including those with intensive forms of land use, show in general a low export of nutrients compared to North American and European catchments, certain land use practices may still have a detrimental effect on the coastal environment. Numerous studies are reported on nutrient cycling and associated processes on a catchment scale in the Northern Hemisphere. Comparable studies in Australia, in particular in subtropical regions are, however, limited and there is a paucity in the data, in particular for inorganic and organic forms of nitrogen and phosphorus; these nutrients are important limiting factors in surface waters to promote algal blooms. Therefore, the monitoring of N and P and understanding the sources and pathways of these nutrients within a catchment is important in coastal zone management. Although Australia is the driest continent, in subtropical regions such as southeast Queensland, rainfall patterns have a significant effect on runoff and thus the nutrient cycle at a catchment scale. Increasingly, these rainfall patterns are becoming variable. The monitoring of these climatic conditions and the hydrological response of agricultural catchments is therefore also important to reduce the anthropogenic effects on surface and groundwater quality. This study consists of an integrated hydrological–hydrochemical approach that assesses N and P in an environment with multiple land uses. The main aim is to determine the nutrient cycle within a representative coastal catchment in southeast Queensland, the Elimbah Creek catchment. In particular, the investigation confirms the influence associated with forestry and agriculture on N and P forms, sources, distribution and fate in the surface and groundwaters of this subtropical setting. In addition, the study determines whether N and P are subject to transport into the adjacent estuary and thus into the marine environment; also considered is the effect of local topography, soils and geology on N and P sources and distribution. The thesis is structured on four components individually reported. The first paper determines the controls of catchment settings and processes on stream water, riverbank sediment, and shallow groundwater N and P concentrations, in particular during the extended dry conditions that were encountered during the study. Temporal and spatial factors such as seasonal changes, soil character, land use and catchment morphology are considered as well as their effect on controls over distributions of N and P in surface waters and associated groundwater. A total number of 30 surface and 13 shallow groundwater sampling sites were established throughout the catchment to represent dominant soil types and the land use upstream of each sampling location. Sampling comprises five rounds and was conducted over one year between October 2008 and November 2009. Surface water and groundwater samples were analysed for all major dissolved inorganic forms of N and for total N. Phosphorus was determined in the form of dissolved reactive P (predominantly orthophosphate) and total P. In addition, extracts of stream bank sediments and soil grab samples were analysed for these N and P species. Findings show that major storm events, in particular after long periods of drought conditions, are the driving force of N cycling. This is expressed by higher inorganic N concentrations in the agricultural subcatchment compared to the forested subcatchment. Nitrate N is the dominant inorganic form of N in both the surface and groundwaters and values are significantly higher in the groundwaters. Concentrations in the surface water range from 0.03 to 0.34 mg N L..1; organic N concentrations are considerably higher (average range: 0.33 to 0.85 mg N L..1), in particular in the forested subcatchment. Average NO3-N in the groundwater has a range of 0.39 to 2.08 mg N L..1, and organic N averages between 0.07 and 0.3 mg N L..1. The stream bank sediments are dominated by organic N (range: 0.53 to 0.65 mg N L..1), and the dominant inorganic form of N is NH4-N with values ranging between 0.38 and 0.41 mg N L..1. Topography and soils, however, were not to have a significant effect on N and P concentrations in waters. Detectable phosphorus in the surface and groundwaters of the catchment is limited to several locations typically in the proximity of areas with intensive animal use; in soil and sediments, P is negligible. In the second paper, the stable isotopes of N (14N/15N) and H2O (16O/18O and 2H/H) in surface and groundwaters are used to identify sources of dissolved inorganic and organic N in these waters, and to determine their pathways within the catchment; specific emphasis is placed on the relation of forestry and agriculture. Forestry is predominantly concentrated in the northern subcatchment (Beerburrum Creek) while agriculture is mainly found in the southern subcatchment (Six Mile Creek). Results show that agriculture (horticulture, crops, grazing) is the main source of inorganic N in the surface waters of the agricultural subcatchment, and their isotopic signature shows a close link to evaporation processes that may occur during water storage in farm dams that are used for irrigation. Groundwaters are subject to denitrification processes that may result in reduced dissolved inorganic N concentrations. Soil organic matter delivers most of the inorganic N to the surface water in the forested subcatchment. Here, precipitation and subsequently runoff is the main source of the surface waters. Groundwater in this area is affected by agricultural processes. The findings also show that the catchment can attenuate the effects of anthropogenic land use on surface water quality. Riparian strips of natural remnant vegetation, commonly 50 to 100 m in width, act as buffer zones along the drainage lines in the catchment and remove inorganic N from the soil water before it enters the creek. These riparian buffer zones are common in most agricultural catchments of southeast Queensland and are indicated to reduce the impact of agriculture on stream water quality and subsequently on the estuary and marine environments. This reduction is expressed by a significant decrease in DIN concentrations from 1.6 mg N L..1 to 0.09 mg N L..1, and a decrease in the �15N signatures from upstream surface water locations downstream to the outlet of the agricultural subcatchment. Further testing is, however, necessary to confirm these processes. Most importantly, the amount of N that is transported to the adjacent estuary is shown to be negligible. The third and fourth components of the thesis use a hydrological catchment model approach to determine the water balance of the Elimbah Creek catchment. The model is then used to simulate the effects of land use on the water balance and nutrient loads of the study area. The tool that is used is the internationally widely applied Soil and Water Assessment Tool (SWAT). Knowledge about the water cycle of a catchment is imperative in nutrient studies as processes such as rainfall, surface runoff, soil infiltration and routing of water through the drainage system are the driving forces of the catchment nutrient cycle. Long-term information about discharge volumes of the creeks and rivers do, however, not exist for a number of agricultural catchments in southeast Queensland, and such information is necessary to calibrate and validate numerical models. Therefore, a two-step modelling approach was used to calibrate and validate parameters values from a near-by gauged reference catchment as starting values for the ungauged Elimbah Creek catchment. Transposing monthly calibrated and validated parameter values from the reference catchment to the ungauged catchment significantly improved model performance showing that the hydrological model of the catchment of interest is a strong predictor of the water water balance. The model efficiency coefficient EF shows that 94% of the simulated discharge matches the observed flow whereas only 54% of the observed streamflow was simulated by the SWAT model prior to using the validated values from the reference catchment. In addition, the hydrological model confirmed that total surface runoff contributes the majority of flow to the surface water in the catchment (65%). Only a small proportion of the water in the creek is contributed by total base-flow (35%). This finding supports the results of the stable isotopes 16O/18O and 2H/H, which show the main source of water in the creeks is either from local precipitation or irrigation waters delivered by surface runoff; a contribution from the groundwater (baseflow) to the creeks could not be identified using 16O/18O and 2H/H. In addition, the SWAT model calculated that around 68% of the rainfall occurring in the catchment is lost through evapotranspiration reflecting the prevailing long-term drought conditions that were observed prior and during the study. Stream discharge from the forested subcatchment was an order of magnitude lower than discharge from the agricultural Six Mile Creek subcatchment. A change in land use from forestry to agriculture did not significantly change the catchment water balance, however, nutrient loads increased considerably. Conversely, a simulated change from agriculture to forestry resulted in a significant decrease of nitrogen loads. The findings of the thesis and the approach used are shown to be of value to catchment water quality monitoring on a wider scale, in particular the implications of mixed land use on nutrient forms, distributions and concentrations. The study confirms that in the tropics and subtropics the water balance is affected by extended dry periods and seasonal rainfall with intensive storm events. In particular, the comprehensive data set of inorganic and organic N and P forms in the surface and groundwaters of this subtropical setting acquired during the one year sampling program may be used in similar catchment hydrological studies where these detailed information is missing. Also, the study concludes that riparian buffer zones along the catchment drainage system attenuate the transport of nitrogen from agricultural sources in the surface water. Concentrations of N decreased from upstream to downstream locations and were negligible at the outlet of the catchment.

Water Sensitive Urban Design (WSUD) application auditing

Background WSUD implementation in the Gold Coast City Council area commenced more than a decade ago. As a result, Council is expected to be in possession of WSUD assets valued at over tens of million dollars. The Gold Coast City Council is responsible for the maintenance and long-term management of these WSUD assets. Any shortcoming in implementation of best WSUD practices can potentially result in substantial liabilities and ineffective expenditure for the Council in addition to reduced efficiencies and outcomes. This highlights the importance of periodic auditing of WSUD implementation. Project scope The overall study entailed the following tasks: * A state-of-the-art literature review of the conceptual hydraulic and water quality treatment principles, current state of knowledge in relation to industry standards, best practice and identification of knowledge gaps in relation to maintenance and management practices and potential barriers to the implementation of WSUD. * Council stakeholder interviews to understand current practical issues in relation to the implementation of WSUD and the process of WSUD application from development application approval to asset management. * Field auditing of selected WSUD systems for condition assessment and identification of possible strengths and weaknesses in implementation. * Review of the Land Development Guidelines in order to identify any gaps and to propose recommendations for improvement. Conclusions Given below is a consolidated summary of the findings of the study undertaken. State-of-the-art literature review Though the conceptual framework for WSUD implementation is well established, the underlying theoretical knowledge underpinning the treatment processes and maintenance regimes and life cycle costing are still not well understood. Essentially, these are the recurring themes in the literature, namely, the inadequate understanding of treatment processes and lack of guidance to ensure specificity of maintenance regimes and life cycle costing of WSUDs. The fundamental barriers to successful WSUD implementation are: * Lack of knowledge transfer – This essentially relates to the lack of appropriate dissemination of research outcomes and the common absence of protocols for knowledge transfer within the same organisation. * Cultural barriers – These relate to social and institutional factors, including institutional inertia and the lack of clear understanding of the benefits. * Fragmented responsibilities – This results from poor administrative integration within local councils in relation to WSUDs. * Technical barriers – These relate to lack of knowledge on operational and maintenance practices which is compounded by model limitations and the lack of long-term quantitative performance evaluation data. * Lack of engineering standards – Despite the availability of numerous guidelines which are non-enforceable and can sometimes be confusing, there is a need for stringent engineering standards. The knowledge gaps in relation to WSUDs are only closing very slowly. Some of the common knowledge gaps identified in recent publications have been recognised almost a decade ago. The key knowledge gaps identified in the published literature are: * lack of knowledge on operational and maintenance practices; * lack of reliable methodology for identifying life cycle issues including costs; * lack of technical knowledge on system performance; * lack of guidance on retrofitting in existing developments. Based on the review of barriers to WSUD implementation and current knowledge gaps, the following were identified as core areas for further investigation: * performance evaluation of WSUD devices to enhance model development and to assess their viability in the context of environmental, economic and social drivers; establishing realistic life cycle costs to strengthen maintenance and asset management practices; * development of guidelines specific to retrofitting in view of the unique challenges posed by existing urban precincts together with guidance to ensure site specificity; establishment of a process for knowledge translation for enhancing currently available best practice guidelines; * identification of drivers and overcoming of barriers in the areas of institutional fragmentation, knowledge gaps and awareness of WSUD practices. GCCC stakeholder interviews Fourteen staff members involved in WSUD systems management in the Gold Coast City Council, representing four Directorates were interviewed using a standard questionnaire. The primary issues identified by the stakeholders were: * standardisation of WSUD terminology; * clear protocols for safeguarding devices during the construction phase; * engagement of all council stakeholders in the WSUD process from the initial phase; * limitations in the Land Development Guidelines; * ensuring public safety through design; * system siting to avoid conflicts with environmental and public use of open space; * provision of adequate access for maintenance; * integration of social and ecosystem issues to ensure long-term viability of systems in relation to both, vandalism and visual recreation; * lack of performance monitoring and inadequacy of the maintenance budget; * lack of technical training for staff involved in WSUD design approvals and maintenance; incentives for developers for acting responsibly in stormwater management. Field auditing of WSUD systems A representative cross section of WSUD systems in the Gold Coast were audited in the field. The following strengths and weaknesses in WSUD implementation were noted: * The implementation of WSUD systems in the field is not consistent. * The concerns raised by the stakeholders during the interviews in relation to WSUD implementation was validated from the observations from the field auditing, particularly in relation to the following: * safeguarding of devices during the construction phase * public safety * accessibility for maintenance * lack of performance monitoring by Council to assess system performance * inadequate maintenance of existing systems to suit site specific requirements. * A treatment train approach is not being consistently adopted. * Most of the systems audited have satisfactorily catered for public safety. Accessibility for maintenance has been satisfactorily catered for in most of the systems that were audited. * Systems are being commissioned prior to construction activities being substantially completed. * The hydraulic design of most systems appears to be satisfactory. * The design intent of the systems is not always clear. Review of Land Development Guidelines The Land Development Guidelines (TDG) was extensively reviewed and the following primary issues were noted in relation to WSUD implementation: * the LDG appears to have been prepared primarily to provide guidance to developers. It is not clear to what extent the guidelines are applicable to Council staff involved in WSUD maintenance and management; * Section 13 is very voluminous and appears to be a compilation of a series of individual documents resulting in difficulties in locating specific information, a lack of integration and duplication of information; * the LDG has been developed with a primary focus on new urban precinct development and the retrofitting of systems in existing developments has not been specifically discussed; * WSUDs are discussed in two different sections in the LDG and it is not clear which section takes precedence as there are inconsistencies between the two sections; there is inconsistent terminology being used; * there is a need for consolidation of information provided in different sections in the LDG; * there are inconsistencies in the design criteria provided; * there is a need for regular updating of the LDG to ensure that the information provided encompasses the state-of-the-art; * there is limited guidance provided for the preparation of maintenance plans and life cycle costing to assist developers in asset handover and to assist Council staff in assessment. * Based on these observations, eleven recommendations have been provided which are discussed below. Additionally, the stakeholder provided the following specific comments during the interviews in relation to the LDG: * lack of flexibility to cover the different stages of the life cycle of the systems; * no differentiation in projects undertaken by developers and Council; * inadequate information with regards to safety issues such as maximum standing water depth, fencing and safety barriers and public access; * lack of detailed design criteria in relation to Crime Prevention through Environmental Design, safety, amenity, environment, surrounding uses and impacts on surroundings; * inadequate information regarding maintenance requirements specific to the assessment and compliance phases; * recommendations for plantings are based primarily on landscape requirements rather than pollutant uptake capability. Recommendations With regards to the Land Development Guidelines, the following specific recommendations are provided: 1. the relevant sections and their extent of applicability to Council should be clearly identified; 2. integration of the different subsections within Section 13 and re-formatting the document for easy reference; 3. the maintenance guidelines provided in Section 13 should be translated to a maintenance manual for guidance of Council staff; 4. should consider extending the Guidelines to specifically encompass retrofitting of WSUD systems to existing urban precincts; 5. Section 3 needs to be revised to be made consistent with Section 13, to ensure priority for WSUD practices in urban precincts and to move away from conventional stormwater drainage design such as kerb and channelling; 6. it would also be good to specify as to which Section takes predominance in relation to stormwater drainage. It is expected that Section 13 would take predominance over the other sections in the LDG; 7. terminology needs to be made consistent to avoid confusion among developers and Council staff. Water Sensitive Urban Design is the term commonly used in Australia for stormwater quality treatment, rather than Stormwater Quality Improvement Devices. This once again underlines the need for ensuring consistency between Section 3 and Section 13; 8. it would also be good if there is a glossary of commonly used terms in relation to WSUD for use by all stakeholders and which should also be reflected in the LDG; 9. consolidation of all WSUD information into one section should be considered together with appropriate indicators in other LDG Sections regarding the availability of WSUD information. Ensuring consistency in the information provided is implied; 10. Section 13 should be updated at regular intervals to ensure the incorporation of the latest in research outcomes and incorporating criteria and guidance based on the state-of-the-art knowledge. The updating could be undertaken, say, in five year cycles. This would help to overcome the current lack of knowledge transfer; 11. the Council should consider commissioning specialised studies to extend the current knowledge base in relation to WSUD maintenance and life cycle costing. Additionally, Recommendation 10 is also applicable in this instance. The following additional recommendations are made based on the state-of-the-art literature review, stakeholder interviews and field auditing of WSUD systems: 1. Performance monitoring of existing systems to assess improvements to water quality, identify modifications and enhancements to improve performance; 2. Appropriate and monitored maintenance during different phases of development of built assets over time is needed to investigate the most appropriate time/phase of development to commission the final WSUD asset. 3. Undertake focussed investigations in the areas of WSUD maintenance and asset management in order to establish more realistic life cycle costs of systems and maintenance schedules; 4. the engagement of all relevant Council stakeholders from the initial stage of concept planning through to asset handover, and ongoing monitoring. This close engagement of internal stakeholders will assist in building a greater understanding of responsibilities and contribute to overcoming constraints imposed by fragmented responsibilities; 5. the undertaking of a public education program to inform the community of the benefits and ecosystem functions of WSUD systems; 6. technical training to impart state-of-the-art knowledge to staff involved in the approval of designs and maintenance and management of WSUD projects; 7. during the construction phase, it is important to ensure that appropriate measures to safeguard WSUD devices are implemented; 8. risks associated with potential public access to open water zones should be minimised with the application of appropriate safety measures; 9. system siting should ensure that potential conflicts are avoided with respect to public and ecosystem needs; 10. integration of social and ecosystem issues to ensure long-term viability of systems; provide incentives to developers who are proactive and responsible in the area of stormwater management.

The location of Ti atom in sodium alanate : an ab initio spin-polarised study

In this work, ab initio spin-polarised Density Functional Theory (DFT) calculations are performed to study the interaction of a Ti atom with a NaAlH4(001) surface. We confirm that an interstitially located Ti atom in the NaAlH4 subsurface is the most energetically favoured configuration as recently reported (Chem. Comm. (17) 2006, 1822). On the NaAlH4(001) surface, the Ti atom is most stable when adsorbed between two sodium atoms with an AlH4 unit beneath. A Ti atom on top of an Al atom is also found to be an important structure at low temperatures. The diffusion of Ti from the Al-top site to the Na-bridging site has a low activation barrier of 0.20 eV and may be activated at the experimental temperatures (∼323 K). The diffusion of a Ti atom into the energetically favoured subsurface interstitial site occurs via the Na-bridging surface site and is essentially barrierless.

A combined environmental scanning electron microscopy and Raman microscopy study of methanol oxidation on silver(I) oxide

The techniques of environmental scanning electron microscopy (ESEM) and Raman microscopy have been used to respectively elucidate the morphological changes and nature of the adsorbed species on silver(I) oxide powder, during methanol oxidation conditions. Heating Ag2O in either water vapour or oxygen resulted firstly in the decomposition of silver(I) oxide to polycrystalline silver at 578 K followed by sintering of the particles at higher temperature. Raman spectroscopy revealed the presence of subsurface oxygen and hydroxyl species in addition to surface hydroxyl groups after interaction with water vapour. Similar species were identified following exposure to oxygen in an ambient atmosphere. This behaviour indicated that the polycrystalline silver formed from Ag2O decomposition was substantially more reactive than silver produced by electrochemical methods. The interaction of water at elevated temperatures subsequent to heating silver(I) oxide in oxygen resulted in a significantly enhanced concentration of subsurface hydroxyl species. The reaction of methanol with Ag2O at high temperatures was interesting in that an inhibition in silver grain growth was noted. Substantial structural modification of the silver(I) oxide material was induced by catalytic etching in a methanol/air mixture. In particular, "pin-hole" formation was observed to occur at temperatures in excess of 773 K, and it was also recorded that these "pin- holes" coalesced to form large-scale defects under typical industrial reaction conditions. Raman spectroscopy revealed that the working surface consisted mainly of subsurface oxygen and surface Ag=O species. The relative lack of sub-surface hydroxyl species suggested that it was the desorption of such moieties which was the cause of the "pin-hole" formation.

In situ imaging of catalytic etching on silver during methanol oxidation conditions by environmental scanning electron microscopy

Polycrystalline silver is used to catalytically oxidise methanol to formaldehyde. This paper reports the results of extensive investigations involving the use of environmental scanning electron microscopy (ESEM) to monitor structural changes in silver during simulated industrial reaction conditions. The interaction of oxygen, nitrogen, and water, either singly or in combination, with a silver catalyst at temperatures up to 973 K resulted in the appearance of a reconstructed silver surface. More spectacular was the effect an oxygen/methanol mixture had on the silver morphology. At a temperature of ca. 713 K pinholes were created in the vicinity of defects as a consequence of subsurface explosions. These holes gradually increased in size and large platelet features were created. Elevation of the catalyst temperature to 843 K facilitated the wholescale oxygen induced restructuring of the entire silver surface. Methanol reacted with subsurface oxygen to produce subsurface hydroxyl species which ultimately formed water in the subsurface layers of silver. The resultant hydrostatic pressure forced the silver surface to adopt a "hill and valley" conformation in order to minimise the surface free energy. Upon approaching typical industrial operating conditions widespread explosions occurred on the catalyst and it was also apparent that the silver surface was extremely mobile under the applied conditions. The interaction of methanol alone with silver resulted in the initial formation of pinholes primarily in the vicinity of defects, due to reaction with oxygen species incorporated in the catalyst during electrochemical synthesis. However, dramatic reduction in the hole concentration with time occurred as all the available oxygen became consumed. A remarkable correlation between formaldehyde production and hole concentration was found.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

First flush behaviour in urban residential catchments

The current state of knowledge in relation to first flush does not provide a clear understanding of the role of rainfall and catchment characteristics in influencing this phenomenon. This is attributed to the inconsistent findings from research studies due to the unsatisfactory selection of first flush indicators and how first flush is defined. The research study discussed in this thesis provides the outcomes of a comprehensive analysis on the influence of rainfall and catchment characteristics on first flush behaviour in residential catchments. Two sets of first flush indicators are introduced in this study. These indicators were selected such that they are representative in explaining in a systematic manner the characteristics associated with first flush. Stormwater samples and rainfall-runoff data were collected and recorded from stormwater monitoring stations established at three urban catchments at Coomera Waters, Gold Coast, Australia. In addition, historical data were also used to support the data analysis. Three water quality parameters were analysed, namely, total suspended solids (TSS), total phosphorus (TP) and total nitrogen (TN). The data analyses were primarily undertaken using multi criteria decision making methods, PROMETHEE and GAIA. Based on the data obtained, the pollutant load distribution curve (LV) was determined for the individual rainfall events and pollutant types. Accordingly, two sets of first flush indicators were derived from the curve, namely, cumulative load wash-off for every 10% of runoff volume interval (interval first flush indicators or LV) from the beginning of the event and the actual pollutant load wash-off during a 10% increment in runoff volume (section first flush indicators or P). First flush behaviour showed significant variation with pollutant types. TSS and TP showed consistent first flush behaviour. However, the dissolved fraction of TN showed significant differences to TSS and TP first flush while particulate TN showed similarities. Wash-off of TSS, TP and particulate TN during the first 10% of the runoff volume showed no influence from corresponding rainfall intensity. This was attributed to the wash-off of weakly adhered solids on the catchment surface referred to as "short term pollutants" or "weakly adhered solids" load. However, wash-off after 10% of the runoff volume showed dependency on the rainfall intensity. This is attributed to the wash-off of strongly adhered solids being exposed when the weakly adhered solids diminish. The wash-off process was also found to depend on rainfall depth at the end part of the event as the strongly adhered solids are loosened due to impact of rainfall in the earlier part of the event. Events with high intensity rainfall bursts after 70% of the runoff volume did not demonstrate first flush behaviour. This suggests that rainfall pattern plays a critical role in the occurrence of first flush. Rainfall intensity (with respect to the rest of the event) that produces 10% to 20% runoff volume play an important role in defining the magnitude of the first flush. Events can demonstrate high magnitude first flush when the rainfall intensity occurring between 10% and 20% of the runoff volume is comparatively high while low rainfall intensities during this period produces low magnitude first flush. For events with first flush, the phenomenon is clearly visible up to 40% of the runoff volume. This contradicts the common definition that first flush only exists, if for example, 80% of the pollutant mass is transported in the first 30% of runoff volume. First flush behaviour for TN is different compared to TSS and TP. Apart from rainfall characteristics, the composition and the availability of TN on the catchment also play an important role in first flush. The analysis confirmed that events with low rainfall intensity can produce high magnitude first flush for the dissolved fraction of TN, while high rainfall intensity produce low dissolved TN first flush. This is attributed to the source limiting behaviour of dissolved TN wash-off where there is high wash-off during the initial part of a rainfall event irrespective of the intensity. However, for particulate TN, the influence of rainfall intensity on first flush characteristics is similar to TSS and TP. The data analysis also confirmed that first flush can occur as high magnitude first flush, low magnitude first flush or non existence of first flush. Investigation of the influence of catchment characteristics on first flush found that the key factors that influence the phenomenon are the location of the pollutant source, spatial distribution of the pervious and impervious surfaces in the catchment, drainage network layout and slope of the catchment. This confirms that first flush phenomenon cannot be evaluated based on a single or a limited set of parameters as a number of catchment characteristics should be taken into account. Catchments where the pollutant source is located close to the outlet, a high fraction of road surfaces, short travel time to the outlet, with steep slopes can produce high wash-off load during the first 50% of the runoff volume. Rainfall characteristics have a comparatively dominant impact on the wash-off process compared to the catchment characteristics. In addition, the pollutant characteristics also should be taken into account in designing stormwater treatment systems due to different wash-off behaviour. Analysis outcomes confirmed that there is a high TSS load during the first 20% of the runoff volume followed by TN which can extend up to 30% of the runoff volume. In contrast, high TP load can exist during the initial and at the end part of a rainfall event. This is related to the composition of TP available for the wash-off.

Complications of perioperative warfarin therapy in total knee arthroplasty

Patients presenting for knee replacement on warfarin for medical reasons often require higher levels of anticoagulation peri-operatively than primary thromboprophylaxis and may require bridging therapy with heparin. We performed a retrospective case control study on 149 consecutive primary knee arthroplasty patients to investigate whether anti-coagulation affected short-term outcomes. Specific outcome measures indicated significant increases in prolonged wound drainage (26.8% of cases vs 7.3% of controls, p<0.001); superficial infection (16.8% vs 3.3%, p<0.001); deep infection (6.0% vs 0%, p<0.001); return-to-theatre for washout (4.7% vs 0.7%, p=0.004); and revision (4.7% vs 0.3%, p=0.001). Management of patients on long-term warfarin therapy following TKR is particularly challenging, as the surgeon must balance risk of thromboembolism against post-operative complications on an individual patient basis in order to optimise outcomes.

Controls on mid-Holocene fringing reef growth and termination in a high latitude, estuarine setting, Wellington Point, Southeast Queensland

Several fringing coral reefs in Moreton Bay, Southeast Queensland, some 300 km south of the Great Barrier Reef (GBR), are set in a relatively high latitude, estuarine environment that is considered marginal for coral growth. Previous work indicated that these marginal reefs, as with many fringing reefs of the inner GBR, ceased accreting in the mid-Holocene. This research presents for the first time data from the subsurface profile of the mid-Holocene fossil reef at Wellington Point comprising U/Th dates of in situ and framework corals, and trace element analysis from the age constrained carbonate fragments. Based on trace element proxies the palaeo-water quality during reef accretion was reconstructed. Results demonstrate that the reef initiated more than 7,000 yr BP during the post glacial transgression, and the initiation progressed to the west as sea level rose. In situ micro-atolls indicate that sea level was at least 1 m above present mean sea level by 6,680 years ago. The reef remained in "catch-up" mode, with a seaward sloping upper surface, until it stopped aggrading abruptly at ca 6,000 yr BP; no lateral progradation occurred. Changes in sediment composition encountered in the cores suggest that after the laterite substrate was covered by the reef, most of the sediment was produced by the carbonate factory with minimal terrigenous influence. Rare earth element, Y and Ba proxies indicate that water quality during reef accretion was similar to oceanic waters, considered suitable for coral growth. A slight decline in water quality on the basis of increased Ba in the later stages of growth may be related to increased riverine input and partial closing up of the bay due to either tidal delta progradation, climatic change and/or slight sea level fall. The age data suggest that termination of reef growth coincided with a slight lowering of sea level, activation of ENSO and consequent increase in seasonality, lowering of temperatures and the constrictions to oceanic flushing. At the cessation of reef accretion the environmental conditions in the western Moreton Bay were changing from open marine to estuarine. The living coral community appears to be similar to the fossil community, but without the branching Acropora spp. that were more common in the fossil reef. In this marginal setting coral growth periods do not always correspond to periods of reef accretion due to insufficient coral abundance. Due to several environmental constraints modern coral growth is insufficient for reef growth. Based on these findings Moreton Bay may be unsuitable as a long term coral refuge for most species currently living in the GBR.

The structured and practical approach in development of decision support system for consultant selection in public sector infrastructure project

Nowadays, most of the infrastructure development projects undertaken are complex in nature. Practically, public clients who do not have a good understanding of the design and management may suffer severe losses, especially for infrastructure projects. There is a need for luring the right consultant to secure client's investment in infrastructure developments. Throughout the project life cycle, consultants play vital role from the inception to completion stage of a project. A few studies in Malaysia show that infrastructure projects involving irrigation and drainage have experience problems such as poor workmanship, delay and cost overrun due to the consultant's inability or the client incompetence of recruiting consultants in time. This highlights the need of aided decision making and an efficient system to select the best consultant by using Decision Support System (DSS). On the other hand, recent trends reveal that most DSS in construction only concentrate on decision model development. These models are impractical and unused as they are complicated or difficult for laymen such as project managers to utilize. Thus, this research attempts to develop an efficient DSS for consultant selection namely consultDeSS. Driven by the motivation and research aims, this study deployed Design Science Research Methodology (DSRM) dominant with a combination of case studies at the Malaysian Department of Irrigation and Drainage (DID). Two real projects involving irrigation and drainage infrastructure were used to design, implement and evaluate the artefact. The 3-tier consultDeSS was revised after the evaluation and the design was significantly improved based on user feedback. By developing desirable tools that fit client's needs will enhance the productivity and minimize conflict within groups and organisations. The tool is more usable and efficient compared to previous studies in construction. Thus, this research has demonstrated a purposeful artefact with a practical and valid structured development approach that is applicable in a variety of problems in construction discipline.

Impacts of climatic factors on evolution of molecular diversity and the natural distribution of wild stocks of the giant freshwater prawn (Macrobrachium rosenbergii)

Natural distributions of most freshwater taxa are restricted geographically, a pattern that reflects dispersal limitation. Macrobrachium rosenbergii is unusual because it occurs naturally in rivers from near Pakistan in the west, across India and Bangladesh to the Malay Peninsula, and across the Sunda Shelf and Indonesian archipelago to western Java. Individuals cannot tolerate full marine conditions, so dispersal between river drainage basins must occur at limited geographical scales when ecological or climatic factors are favorable. We examined molecular diversity in wild populations of M. rosenbergii across its complete natural range to document patterns of diversity and to relate them to factors that have driven evolution of diversity in this species. We found 3 clades in the mitochondrial deoxyribonucleic acid (mtDNA) data set that corresponded geographically with eastern, central, and western sets of haplotypes that last shared a common ancestor 1 × 106 y ago. The eastern clade was closest to the common ancestor of all 3 clades and to the common ancestor with its congener, Macrobrachium spinipes, distributed east of Huxley's Line. Macrobrachium rosenbergii could have evolved in the western Indonesian archipelago and spread westward during the early to mid-Pleistocene to India and Sri Lanka. Additional groups identified in the nuclear DNA data set in the central and western clades probably indicate secondary contact via dispersal between regions and modern introductions that have mixed nuclear and mtDNA genes. Pleistocene sea-level fluctuations can explain dispersal across the Indonesian archipelago and parts of mainland southeastern Asia via changing river drainage connections in shallow seas on wide continental shelves. At the western end of the modern distribution where continental shelves are smaller, intermittent freshwater plumes from large rivers probably permitted larval dispersal across inshore areas of lowered salinity.

First full-scale trials of pebble matrix filtration

Protecting slow sand filters from high turbidity waters by pre-treatment using Pebble Matrix Filtration (PMF) has been studied in the laboratory at University College London followed by pilot field trials in Papua New Guinea and Serbia. Subsequently, the construction of two full-scale PMF units, one out of concrete (4.8m x4.8m x 3.0m high) and the other using pre-cast Ferro-cement panels (900mm x 1600mm x 20mm thick) with an effective diameter of 4.7m and 3m height, and the combined effective plan area of 40 m2 was completed to protect an existing Slow Sand Filter system at the National Water Supply Drainage Board (NWSDB) in Sri Lanka. Although the plant was completed in April 2008 due to some major repairs to address some leaks and other construction defects in both filters, monitoring was intermittent until November 2008. The results on the plant performance are presented here along with some of the construction problems encountered during the project.

An assessment of the geographical scale of recurrent gene flow in wild populations of two species of Mekong River carps (Henicorhynchus spp.)

The Mekong is the most productive river fishery in the world, and such as, the Mekong River Basin (MRB) is very important to very large human populations across the region as a source of revenue (through fishing and marketing of aquatic resources products) and as the major source for local animal protein. Threats to biodiversity in the MRB, either to the fishery sector itself or to other sectors are a major concern, even though currently, fisheries across this region are still very productive. If not managed properly however, fish population declines will cause significant economic impact and affect livelihoods of local people and will have a major impact on food security and nutrition. Biodiversity declines will undoubtedly affect food security, income and socio-economic status of people in the MRB that depend on aquatic resources. This is an indicator of unsustainable development and hence should be avoided. Genetic diversity (biodiversity) that can be measured using techniques based on DNA markers; refers to variation within and among populations within the same species or reproductive units. In a population, new genetic variation is generated by sexual recombination contributed by individuals with mutations in genes and chromosomes. Over time, populations of a species that are not reproducing together will diverge as differential impacts of selection and genetic drift change their genetic attributes. For mud carp (Henicorhynchus spp.), understanding the status of breeding units in the MRB will be important for their long term persistence, sustainability and for implementing effective management strategies. Earlier analysis of stock structure in two economically important mud carp species (Henicorhynchus siamensis and H. lobatus) in the MRB completed with mtDNA markers identified a number of populations of both species where gene flow had apparently been interrupted or reduced but applying these data directly to management unit identification is potentially compromised because information was only available about female dispersal patterns. The current study aimed to address this problem and to fully assess the extent of current gene flow (nDNA) and reproductive exchange among selected wild populations of two species of carp (Henicorhynchus spp.) of high economic importance in the MRB using combined mtDNA and nDNA markers. In combination, the data can be used to define effective management units for each species. In general, nDNA diversity for H. lobatus (with average allelic richness (A) 7.56 and average heterozygosity (Ho) 0.61) was very similar to that identified for H. siamensis (A = 6.81 and Ho = 0.75). Both mud carp species show significant but low FST estimates among populations as a result of lower genetic diversity among sampled populations compared with genetic diversity within populations that may potentially mask any 'real' population structure. Overall, population genetic structure patterns from mtDNA and nDNA in both Henicorhynchus species were largely congruent. Different population structures however, were identified for the two Henicorhynchus species across the same geographical area. Apparent co-similarity in morphology and co-distribution of these two relatively closely related species does not apparently imply parallel evolutionary histories. Differences in each species population structure likely reflect historical drainage rearrangement of the Mekong River. The data indicate that H. siamensis is likely to have occupied the Mekong system for much longer than has H. lobatus in the past. Two divergent stocks were identified for H. lobatus in the MRB below the Khone Falls while a single stock had been evident in the earlier mtDNA study. This suggests that the two Henicorhynchus species may possess different life history traits and that different patterns of gene flow has likely influenced modern genetic structure in these close congeners. In combination, results of the earlier mtDNA and the current study have implications for effective management of both Henicorhynchus species across the MRB. Currently, both species are essentially treated as a single management unit in this region. This strategy may be appropriate for H. lobatus as a single stock was evident in the main stream of the MRB, but may not be appropriate for H. siamensis as more than a single stock was identified across the same range for this species. Management strategies should consider this difference to conserve overall biodiversity (local discrete populations) and this will include maintaining natural habitat and migration pathways, provision of fish sanctuaries (refuges) and may also require close monitoring of any stock declines, a signal that may require effective recovery strategies.

Wet tropics reef rescue impact report 2009

The Wet Tropics region has a unique water asset and is also considered a priority region for the improvement of water quality entering the Great Barrier Reef due to a combination of high rainfall, intensive agricultural use, urban areas and the proximity of valuable reef assets to the coast. Agricultural activities are one of many identified threats to water quality and water flows in the Wet Tropics in terms of sediment and pollutant-related water quality decline. Information describing the current state of agricultural management practices across the region is patchy at best. Based on the best available information on agricultural management practices in the Wet Tropics in 2008, it is clear that opportunities exist to improve nutrient, sediment and pesticide management practice to reduce the impact on the water asset and the Great Barrier Reef. Based on current understandings of practices and the relationship between practices and reef water quality, the greatest opportunities for improved water quality are as follows: · nutrients – correct rate and the placement of fertilisers; · pesticides – improve weed control planning, herbicide rates and calibration practice; and · soil and sediment – implement new farming system practices. The 2008-09 Reef Rescue program sought to accelerate the rate of adoption of improved management practices and through Terrain invested $6.8M in the 2008-09 year for: · landholder water quality improvement incentive payments; · cross regional catchment repair of wetlands and riparian lands in areas of high sediment or nutrient loss; and · partnerships in the region to lever resources and support for on-ground practice change. The program delivered $3,021,999 in onground incentives to landholders in the Wet Tropics to improve farm practices from D or C level to B or A level. The landholder Water Quality Incentives Grants program received 300 individual applications for funding and funded 143 individual landholders to implement practice change across 36,098 ha of farm land. It is estimated that the Reef Rescue program facilitated practice change across 21% of the cane industry, and 20% of the banana industry. The program levered an additional $2,441,166 in landholder cash contributions and a further $907,653 in non-cash in-kind contributions bringing the total project value of the landholder grants program in the Wet Tropics to $6,370,819. Most funded projects targeted multiple water quality objectives with a focus on nutrient and sediment reduction. Of the 143 projects funded, 115 projects addressed nutrient management either as the primary focus or in combination with strategies that targeted other water quality objectives. Overall, 82 projects addressed two or more water quality targets. Forty-five percent of incentive funds were allocated to new farming system practices (direct drill legumes, zonal tillage equipment, permanent beds, min till planting equipment, GPS units, laser levelling), followed by 24% allocated to subsurface fertiliser applicators (subsurface application of fertiliser using a stool splitter or beside the stool, at the correct Six Easy Steps rate). As a result, Terrain estimates that the incentive grants achieved considerable reductions in nitrogen, phosphorus, sediment and pesticide loads. The program supported nutrient management training of 167 growers managing farms covering over 20% of the area harvested in 2008, and 18 industry advisors and resellers. This resulted in 115 growers (155 farms) developing nutrient management plans. The program also supported Integrated Weed Management training of 80 growers managing farms covering 8% of the area harvested in 2008, and 6 industry advisors and resellers. This report, which draws on the best available Reef Rescue Management Monitoring, Evaluation, Reporting, and Improvement (MERI) information to evaluate program performance and impact on water quality outcomes, is the first in a series of annual reports that will assess and evaluate the impact of the Reef Rescue program on agricultural practices and water quality outcomes. The assessment is predominantly focused on the cane industry because of data availability. In the next stage, efforts will expand to: · improve practice data for the banana and grazing industry; · gain a better understanding of the water quality trends and the factors influencing them in the Wet Tropics; in particular work will focus on linking the results of the Paddock to Reef monitoring program and practice change data to assess program impact; · enhance estimations of the impact of practice change on pollutant loads from agricultural land use; · gain a better understanding of the extent of ancillary practice (change not directly funded) resulting from Reef Rescue training/ education/communication programs; and · provide a better understanding of the economic cost of practice change across the Wet Tropics region. From an ecological perspective, water quality trends and the factors that may be contributing to change, require further investigation. There is a critical need to work towards an enhanced understanding of the link between catchment land management practice change and reef water quality, so that reduced nutrient, sediment, and pesticide discharge to the Great Barrier Reef can be quantified. This will also assist with future prioritisation of grants money to agricultural industries, catchments and sub catchments. From a social perspective, the program has delivered significant water quality benefits from landholder education and training. It is believed that these activities are giving landholders the information and tools to implement further lasting change in their production systems and in doing so, creating a change in attitude that is supportive and inclusive of Natural Resource Management (NRM). The program in the Wet Tropics has also considerably strengthened institutional partnerships for NRM, particularly between NRM and industry and extension organisations. As a result of the Reef Rescue program, all institutions are actively working together to collectively improve water quality. The Reef Rescue program is improving water quality entering the Great Barrier Reef Lagoon by catalysing substantial activity in the Wet Tropics region to improve land management practices and reduce the water quality impact of agricultural landscapes. The solid institutional partnerships between the regional body, industry, catchment and government organisations have been fundamental to the successful delivery of the landholder grant and catchment rehabilitation programs. Landholders have generally had a positive perception and reaction to the program, its intent, and the practical, focused nature of grant-based support. Demand in the program was extremely high in 2008-09 and is expected to increase in 2009-2010.