Assessment of pre- and post-flood groundwater recharge via 3D visualisation, Lockyer Valley, southeast Queensland

The Lockyer Valley in southeast Queensland supports important and intensive irrigation which is dependant on the quality and availability of groundwater. Prolonged drought conditions from ~1997 resulted in a depletion of the alluvial aquifers, and concern for the long-term sustainability of this resource. By 2008, many areas of the valley were at < 20% of storage. Some relief occurred with rain events in early 2009, then in December 2010 - January 2011, most of southeast Queensland experienced unprecedented flooding. These storm-based events have caused a shift in research focus from investigations of drought conditions and mitigation to flood response analysis. For the alluvial aquifer system of the valley, a preliminary assessment of groundwater observation bore data, prior to and during the flood, indicates that there is a spatially variable aquifer response. While water levels in some bores screened in unconfined shallow aquifers have recovered by more than 10 m within a short period of time (months), others show only a small or moderate response. Measurements of pre- and post-flood groundwater levels and high-resolution time-series records from data loggers are considered within the framework of a 3D geological model of the Lockyer Valley using Groundwater Visualisation System(GVS). Groundwater level fluctuations covering both drought and flood periods are used to estimate groundwater recharge using the water table fluctuation method (WTF), supplemented by estimates derived using chloride mass balance. The presentation of hydraulic and recharge information in a 3D format has considerable advantages over the traditional 2D presentation of data. The 3D approach allows the distillation of multiple types of information(topography, geological, hydraulic and spatial) into one representation that provides valuable insights into the major controls of groundwater flow and recharge. The influence of aquifer lithology on the spatial variability of groundwater recharge is also demonstrated.

Exploiting the 1,2,3-triazolium motif in anion-templated formation of a bromide-selective rotaxane host assembly

Stimulated by the efficacy of copper (I) catalysed Huisgen-type 1,3-dipolar cycloaddition of terminal alkynes and organic azides to generate 1,4-disubstituted 1,2,3-triazole derivatives, the importance of ‘click’ chemistry in the synthesis of organic and biological molecular systems is ever increasing.[1] The mild reaction conditions have also led to this reaction gaining favour in the construction of interlocked molecular architectures.[2-4] In the majority of cases however, the triazole group simply serves as a covalent linkage with no function in the resulting organic molecular framework. More recently a renewed interest has been shown in the transition metal coordination chemistry of triazole ligands.[3, 5, 6] In addition novel aryl macrocyclic and acyclic triazole based oligomers have been shown to recognise halide anions via cooperative triazole C5-H….anion hydrogen bonds.[7] In light of this it is surprising the potential anion binding affinity of the positively charged triazolium motif has not, with one notable exception,[8] been investigated. With the objective of manipulating the unique topological cavities of mechanically bonded molecules for anion recognition purposes, we have developed general methods of using anions to template the formation of interpenetrated and interlocked structures.[9-13] Herein we report the first examples of exploiting the 1,2,3-triazolium group in the anion templated formation of pseudorotaxane and rotaxane assemblies. In an unprecedented discovery the bromide anion is shown to be a superior templating reagent to chloride in the synthesis of a novel triazolium axle containing [2]rotaxane. Furthermore the resulting rotaxane interlocked host system exhibits the rare selectivity preference for bromide over chloride...

The neurokinin 1 receptor antagonist, ezlopitant, reduces appetitive responding for sucrose and ethanol

Abstract Background: The current obesity epidemic is thought to be partly driven by over-consumption of sugar-sweetened diets and soft drinks. Loss-of-control over eating and addiction to drugs of abuse share overlapping brain mechanisms including changes in motivational drive, such that stimuli that are often no longer ‘liked’ are still intensely ‘wanted’ [7,8]. The neurokinin 1 (NK1) receptor system has been implicated in both learned appetitive behaviors and addiction to alcohol and opioids; however, its role in natural reward seeking remains unknown. Methodology/Principal Findings: We sought to determine whether the NK1-receptor system plays a role in the reinforcing properties of sucrose using a novel selective and clinically safe NK1-receptor antagonist, ezlopitant (CJ-11,974), in three animal models of sucrose consumption and seeking. Furthermore, we compared the effect of ezlopitant on ethanol consumption and seeking in rodents. The NK1-receptor antagonist, ezlopitant decreased appetitive responding for sucrose more potently than for ethanol using an operant self-administration protocol without affecting general locomotor activity. To further evaluate the selectivity of the NK1-receptor antagonist in decreasing consumption of sweetened solutions, we compared the effects of ezlopitant on water, saccharin-, and sodium chloride (NaCl) solution consumption. Ezlopitant decreased intake of saccharin but had no effect on water or salty solution consumption. Conclusions/Significance: The present study indicates that the NK1-receptor may be a part of a common pathway regulating the self-administration, motivational and reinforcing aspects of sweetened solutions, regardless of caloric value, and those of substances of abuse. Additionally, these results indicate that the NK1-receptor system may serve as a therapeutic target for obesity induced by over-consumption of natural reinforcers.

Vibrational spectroscopy of the multi anion mineral zykaite Fe4(AsO4)(SO4)(OH)•15H2O – implications for arsenate removal

Some minerals are colloidal and are poorly diffracting . Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of minerals. Among this group of minerals is zykaite with formula Fe4(AsO4)(SO4)(OH)•15H2O. The objective of this research is to determine the molecular structure of the mineral zykaite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO43-, SO42- and water stretching vibrations. The sharp band at 3515 cm-1 is assigned to the stretching vibration of the OH units. This mineral offers a mechanism for the formation of more crystalline minerals such as scorodite and bukovskyite. Arsenate ions can be removed from aqueous systems through the addition of ferric compounds such as ferric chloride. This results in the formation of minerals such as zykaite and pitticite (Fe3+,AsO4,SO4,H2O).

The flammability of metallic materials in normal and reduced gravity

Metallic materials exposed to oxygen-enriched atmospheres – as commonly used in the medical, aerospace, aviation and numerous chemical processing industries – represent a significant fire hazard which must be addressed during design, maintenance and operation. Hence, accurate knowledge of metallic materials flammability is required. Reduced gravity (i.e. space-based) operations present additional unique concerns, where the absence of gravity must also be taken into account. The flammability of metallic materials has historically been quantified using three standardised test methods developed by NASA, ASTM and ISO. These tests typically involve the forceful (promoted) ignition of a test sample (typically a 3.2 mm diameter cylindrical rod) in pressurised oxygen. A test sample is defined as flammable when it undergoes burning that is independent of the ignition process utilised. In the standardised tests, this is indicated by the propagation of burning further than a defined amount, or „burn criterion.. The burn criterion in use at the onset of this project was arbitrarily selected, and did not accurately reflect the length a sample must burn in order to be burning independent of the ignition event and, in some cases, required complete consumption of the test sample for a metallic material to be considered flammable. It has been demonstrated that a) a metallic material.s propensity to support burning is altered by any increase in test sample temperature greater than ~250-300 oC and b) promoted ignition causes an increase in temperature of the test sample in the region closest to the igniter, a region referred to as the Heat Affected Zone (HAZ). If a test sample continues to burn past the HAZ (where the HAZ is defined as the region of the test sample above the igniter that undergoes an increase in temperature of greater than or equal to 250 oC by the end of the ignition event), it is burning independent of the igniter, and should be considered flammable. The extent of the HAZ, therefore, can be used to justify the selection of the burn criterion. A two dimensional mathematical model was developed in order to predict the extent of the HAZ created in a standard test sample by a typical igniter. The model was validated against previous theoretical and experimental work performed in collaboration with NASA, and then used to predict the extent of the HAZ for different metallic materials in several configurations. The extent of HAZ predicted varied significantly, ranging from ~2-27 mm depending on the test sample thermal properties and test conditions (i.e. pressure). The magnitude of the HAZ was found to increase with increasing thermal diffusivity, and decreasing pressure (due to slower ignition times). Based upon the findings of this work, a new burn criterion requiring 30 mm of the test sample to be consumed (from the top of the ignition promoter) was recommended and validated. This new burn criterion was subsequently included in the latest revision of the ASTM G124 and NASA 6001B international test standards that are used to evaluate metallic material flammability in oxygen. These revisions also have the added benefit of enabling the conduct of reduced gravity metallic material flammability testing in strict accordance with the ASTM G124 standard, allowing measurement and comparison of the relative flammability (i.e. Lowest Burn Pressure (LBP), Highest No-Burn Pressure (HNBP) and average Regression Rate of the Melting Interface(RRMI)) of metallic materials in normal and reduced gravity, as well as determination of the applicability of normal gravity test results to reduced gravity use environments. This is important, as currently most space-based applications will typically use normal gravity information in order to qualify systems and/or components for reduced gravity use. This is shown here to be non-conservative for metallic materials which are more flammable in reduced gravity. The flammability of two metallic materials, Inconel® 718 and 316 stainless steel (both commonly used to manufacture components for oxygen service in both terrestrial and space-based systems) was evaluated in normal and reduced gravity using the new ASTM G124-10 test standard. This allowed direct comparison of the flammability of the two metallic materials in normal gravity and reduced gravity respectively. The results of this work clearly show, for the first time, that metallic materials are more flammable in reduced gravity than in normal gravity when testing is conducted as described in the ASTM G124-10 test standard. This was shown to be the case in terms of both higher regression rates (i.e. faster consumption of the test sample – fuel), and burning at lower pressures in reduced gravity. Specifically, it was found that the LBP for 3.2 mm diameter Inconel® 718 and 316 stainless steel test samples decreased by 50% from 3.45 MPa (500 psia) in normal gravity to 1.72 MPa (250 psia) in reduced gravity for the Inconel® 718, and 25% from 3.45 MPa (500 psia) in normal gravity to 2.76 MPa (400 psia) in reduced gravity for the 316 stainless steel. The average RRMI increased by factors of 2.2 (27.2 mm/s in 2.24 MPa (325 psia) oxygen in reduced gravity compared to 12.8 mm/s in 4.48 MPa (650 psia) oxygen in normal gravity) for the Inconel® 718 and 1.6 (15.0 mm/s in 2.76 MPa (400 psia) oxygen in reduced gravity compared to 9.5 mm/s in 5.17 MPa (750 psia) oxygen in normal gravity) for the 316 stainless steel. Reasons for the increased flammability of metallic materials in reduced gravity compared to normal gravity are discussed, based upon the observations made during reduced gravity testing and previous work. Finally, the implications (for fire safety and engineering applications) of these results are presented and discussed, in particular, examining methods for mitigating the risk of a fire in reduced gravity.

An experimental study of a reactive plume in grid turbulence

Experimental results for a reactive non-buoyant plume of nitric oxide (NO) in a turbulent grid flow doped with ozone (O3) are presented. The Damkohler number (Nd) for the experiment is of order unity indicating the turbulence and chemistry have similar timescales and both affect the chemical reaction rate. Continuous measurements of two components of velocity using hot-wire anemometry and the two reactants using chemiluminescent analysers have been made. A spatial resolution for the reactants of four Kolmogorov scales has been possible because of the novel design of the experiment. Measurements at this resolution for a reactive plume are not found in the literature. The experiment has been conducted relatively close to the grid in the region where self-similarity of the plume has not yet developed. Statistics of a conserved scalar, deduced from both reactive and non-reactive scalars by conserved scalar theory, are used to establish the mixing field of the plume, which is found to be consistent with theoretical considerations and with those found by other investigators in non-reative flows. Where appropriate the reactive species means and higher moments, probability density functions, joint statistics and spectra are compared with their respective frozen, equilibrium and reaction-dominated limits deduced from conserved scalar theory. The theoretical limits bracket reactive scalar statistics where this should be so according to conserved scalar theory. Both reactants approach their equilibrium limits with greater distance downstream. In the region of measurement, the plume reactant behaves as the reactant not in excess and the ambient reactant behaves as the reactant in excess. The reactant covariance lies outside its frozen and equilibrium limits for this value of Vd. The reaction rate closure of Toor (1969) is compared with the measured reaction rate. The gradient model is used to obtain turbulent diffusivities from turbulent fluxes. Diffusivity of a non-reactive scalar is found to be close to that measured in non-reactive flows by others.

Stability of hydrotalcites formed from Bayer refinery environmental control processes

Bauxite refinery residues (red mud) are derived from the Bayer process by the digestion of crushed bauxite in concentrated sodium hydroxide at elevated temperatures and pressures. This slurry residue, if untreated, is unsuitable for discharge directly into the environment and is usually stored in tailing dams. The liquid portion has the potential for discharge, but requires pre-treatment before this can occur. The seawater neutralisation treatment facilitates a significant reduction in pH and dissolved metal concentrations, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. The hydrotalcite-like compounds, precipitated during seawater neutralisation, also remove a range of transition metals, oxy-anions and other anionic species through a combination of intercalation and adsorption reactions: smaller anions are intercalated into the hydrotalcite matrix, while larger molecules are adsorbed on the particle surfaces. A phenomenon known as ‘reversion’ can occur if the seawater neutralisation process is not properly controlled. Reversion causes an increase in the pH and dissolved impurity levels of the neutralised effluent, rendering it unsuitable for discharge. It is believed that slow dissolution of components of the red mud residue and compounds formed during the neutralisation process are responsible for reversion. This investigation looked at characterising natural hydrotalcite (Mg6Al2(OH)16(CO3)∙4H2O) and ‘Bayer’ hydrotalcite (synthesised using the seawater neutralisation process) using a variety of techniques including X-ray diffraction, infrared and Raman spectroscopy, and thermogravimetric analysis. This investigation showed that Bayer hydrotalcite is comprised of a mixture of 3:1 and 4:1 hydrotalcite structures and exhibited similar chemical characteristic to the 4:1 synthetic hydrotalcite. Hydrotalcite formed from the seawater neutralisation of Bauxite refinery residues has been found not to cause reversion. Other components in red mud were investigated to determine the cause of reversion and this investigation found three components that contributed to reversion: 1) tricalcium aluminate, 2) hydrocalumite and 3) calcium hydroxide. Increasing the amount of magnesium in the neutralisation process has been found to be successful in reducing reversion.

Sulfate intercalated layered double hydroxides prepared by the reformation effect

The removal of the sulfate anion from water using synthetic hydrotalcite (Mg/Al LDH) was investigated using powder x-ray diffraction (XRD) and thermogravimetric analysis (TG). Synthetic hydrotalcite Mg6Al2(OH)16(CO3)∙4H2O was prepared by the co-precipitation method from aluminum and magnesium chloride salts. The synthetic hydrotalcite was thermally activated to a maximum temperature of 380°C. Samples of thermally activated hydrotalcite where then treated with aliquots of 1000ppm sulfate solution. The resulting products where dried and characterized by XRD and TG. Powder XRD revealed that hydrotalcite had been successfully prepared and that the product obtained after treatment with sulfate solution also conformed well to the reference pattern of hydrotalcite. The d(003) spacing of all samples was found to be within the acceptable region for a LDH structure. TG revealed all products underwent a similar decomposition to that of hydrotalcite. It was possible to propose a reasonable mechanism for the thermal decomposition of a sulfate containing Mg/Al LDH. The similarities in the results may indicate that the reformed hydrotalcite may contain carbonate anion as well as sulfate. Further investigation is required to confirm this.

A study of ionic liquids for dissolution of sugarcane bagasse

Over the last decade, Ionic Liquids (ILs) have been used for the dissolution and derivatization of isolated cellulose. This ability of ILs is now sought for their application in the selective dissolution of cellulose from lignocellulosic biomass, for the manufacture of cellulosic ethanol. However, there are significant knowledge gaps in the understanding of the chemistry of the interaction of biomass and ILs. While imidazolium ILs have been used successfully to dissolve both isolated crystalline cellulose and components of lignocellulosic biomass, phosphonium ILs have not been sufficiently explored for the use in dissolution of lignocellulosic biomass. This thesis reports on the study of the chemistry of sugarcane bagasse with phosphonium ILs. Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO4) are obtained using attenuated total reflectance-Fourier Transform Infra Red (FTIR). Absorption bands related to cellulose, hemicelluloses and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalysed β-aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The quantitative measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm-1 has demonstrated utility and greater precision than the conventional Klason lignin method. The cleavage of lignin β-aryl ether bonds in sugarcane bagasse by the ionic liquid [P66614]Cl, in the presence of catalytic amounts of mineral acid. (ca. 0.4 %). The delignification process of bagasse is studied over a range of temperatures (120 °C to 150 °C) by monitoring the production of β-ketones (indicative of cleavage of β-aryl ethers) using FTIR spectroscopy and by compositional analysis of the undissolved fractions. Maximum delignification is obtained at 150 °C, with 52 % of lignin removed from the original lignin content of bagasse. No delignification is observed in the absence of acid which suggests that the reaction is acid catalysed with the IL solubilising the lignin fragments. The rate of delignification was significantly higher at 150 °C, suggesting that crossing the glass transition temperature of lignin effects greater freedom of rotation about the propanoid carbon-carbon bonds and leads to increased cleavage of β-aryl ethers. An attempt has been made to propose a probable mechanism of delignifcation of bagasse with the phosphonuim IL. All polymeric components of bagasse, a lignocellulosic biomass, dissolve in the hydrophilic ionic liquid (IL) tributylmethylphosphonium methylsulfate ([P4441]MeSO4) with and without a catalytic amount of acid (H2SO4, ca. 0.4 %). The presence of acid significantly increases the extent of dissolution of bagasse in [P4441]MeSO4 (by ca. 2.5 times under conditions used here). The dissolved fractions can be partially recovered by the addition of an antisolvent (water) and are significantly enriched in lignin. Unlike acid catalysed dissolution in the hydrophobic IL tetradecyltrihexylphosphonium chloride there is little evidence of cleavage of β-aryl ether bonds of lignin dissolving in [P4441]MeSO4 (with and without acid), but this mechanism may play some role in the acid catalysed dissolution. The XRD of the undissolved fractions suggests that the IL may selectively dissolve the amorphous cellulose component, leaving behind crystalline material.

ATR-FTIR measurement of biomass components in phosphonium ionic liquids

Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO 4), are obtained using attenuated total reflectance-FTIR. Absorption bands related to cellulose, hemicelluloses, and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO 4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalyzed -aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO 4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm 1 has demonstrated utility. When coupled with the gravimetric Klason lignin method, ATR-FTIR study of reaction mixtures can lead to a better understanding of the delignification process. © 2012 Copyright Taylor and Francis Group, LLC.

Pretreatment of sugarcane bagasse by acid-catalysed process in aqueous ionic liquid solutions

A biomass pretreatment process was developed using acidified ionic liquid (IL) solutions containing 10-30% water. Pretreatment of sugarcane bagasse at 130°C for 30min by aqueous 1-butyl-3-methylimidazolium chloride (BMIMCl) solution containing 1.2% HCl resulted in a glucan digestibility of 94-100% after 72h of enzymatic hydrolysis. HCl was found to be a more effective catalyst than H(2)SO(4) or FeCl(3). Increasing acid concentration (from 0.4% to 1.2%) and reaction temperature (from 90 to 130°C) increased glucan digestibility. The glucan digestibility of solid residue obtained with the acidified BMIMCl solution that was re-used for three times was >97%. The addition of water to ILs for pretreatment could significantly reduce IL solvent costs and allow for increased biomass loadings, making the pretreatment by ILs a more economic proposition.

The persistence of phase-separation in LiFePO4 with two-dimensional Li+ transport : the Cahn-Hilliard-reaction equation and the role of defects

We examine the solution of the two-dimensional Cahn-Hilliard-reaction (CHR) equation in the xy plane as a model of Li+ intercalation into LiFePO4 material. We validate our numerical solution against the solution of the depth-averaged equation, which has been used to model intercalation in the limit of highly orthotropic diffusivity and gradient penalty tensors. We then examine the phase-change behaviour in the full CHR system as these parameters become more isotropic, and find that as the Li+ diffusivity is increased in the x direction, phase separation persists at high currents, even in small crystals with averaged coherency strain included. The resulting voltage curves decrease monotonically, which has previously been considered a hallmark of crystals that fill homogeneously.

Performance evaluation of onsite wastewater treatment : field sampling and preliminary evaluation of results

Background The onsite treatment of sewage and effluent disposal within the premises is widely prevalent in rural and urban fringe areas due to the general unavailability of reticulated wastewater collection systems. Despite the seemingly low technology of the systems, failure is common and in many cases leading to adverse public health and environmental consequences. Therefore it is important that careful consideration is given to the design and location of onsite sewage treatment systems. It requires an understanding of the factors that influence treatment performance. The use of subsurface effluent absorption systems is the most common form of effluent disposal for onsite sewage treatment and particularly for septic tanks. Additionally in the case of septic tanks, a subsurface disposal system is generally an integral component of the sewage treatment process. Therefore location specific factors will play a key role in this context. The project The primary aims of the research project are: • to relate treatment performance of onsite sewage treatment systems to soil conditions at site; • to identify important areas where there is currently a lack of relevant research knowledge and is in need of further investigation. These tasks were undertaken with the objective of facilitating the development of performance based planning and management strategies for onsite sewage treatment. The primary focus of the research project has been on septic tanks. Therefore by implication the investigation has been confined to subsurface soil absorption systems. The design and treatment processes taking place within the septic tank chamber itself did not form a part of the investigation. In the evaluation to be undertaken, the treatment performance of soil absorption systems will be related to the physico-chemical characteristics of the soil. Five broad categories of soil types have been considered for this purpose. The number of systems investigated was based on the proportionate area of urban development within the Brisbane region located on each soil types. In the initial phase of the investigation, though the majority of the systems evaluated were septic tanks, a small number of aerobic wastewater treatment systems (AWTS) were also included. This was primarily to compare the effluent quality of systems employing different generic treatment processes. It is important to note that the number of different types of systems investigated was relatively small. As such this does not permit a statistical analysis to be undertaken of the results obtained. This is an important issue considering the large number of parameters that can influence treatment performance and their wide variability. The report This report is the second in a series of three reports focussing on the performance evaluation of onsite treatment of sewage. The research project was initiated at the request of the Brisbane City Council. The work undertaken included site investigation and testing of sewage effluent and soil samples taken at distances of 1 and 3 m from the effluent disposal area. The project component discussed in the current report formed the basis for the more detailed investigation undertaken subsequently. The outcomes from the initial studies have been discussed, which enabled the identification of factors to be investigated further. Primarily, this report contains the results of the field monitoring program, the initial analysis undertaken and preliminary conclusions. Field study and outcomes Initially commencing with a list of 252 locations in 17 different suburbs, a total of 22 sites in 21 different locations were monitored. These sites were selected based on predetermined criteria. To obtain house owner agreement to participate in the monitoring study was not an easy task. Six of these sites had to be abandoned subsequently due to various reasons. The remaining sites included eight septic systems with subsurface effluent disposal and treating blackwater or combined black and greywater, two sites treating greywater only and six sites with AWTS. In addition to collecting effluent and soil samples from each site, a detailed field investigation including a series of house owner interviews were also undertaken. Significant observations were made during the field investigations. In addition to site specific observations, the general observations include the following: • Most house owners are unaware of the need for regular maintenance. Sludge removal has not been undertaken in any of the septic tanks monitored. Even in the case of aerated wastewater treatment systems, the regular inspections by the supplier is confined only to the treatment system and does not include the effluent disposal system. This is not a satisfactory situation as the investigations revealed. • In the case of separate greywater systems, only one site had a suitably functioning disposal arrangement. The general practice is to employ a garden hose to siphon the greywater for use in surface irrigation of the garden. • In most sites, the soil profile showed significant lateral percolation of effluent. As such, the flow of effluent to surface water bodies is a distinct possibility. • The need to investigate the subsurface condition to a depth greater than what is required for the standard percolation test was clearly evident. On occasion, seemingly permeable soil was found to have an underlying impermeable soil layer or vice versa. The important outcomes from the testing program include the following: • Though effluent treatment is influenced by the physico-chemical characteristics of the soil, it was not possible to distinguish between the treatment performance of different soil types. This leads to the hypothesis that effluent renovation is significantly influenced by the combination of various physico-chemical parameters rather than single parameters. This would make the processes involved strongly site specific. • Generally the improvement in effluent quality appears to take place only within the initial 1 m of travel and without any appreciable improvement thereafter. This relates only to the degree of improvement obtained and does not imply that this quality is satisfactory. This calls into question the value of adopting setback distances from sensitive water bodies. • Use of AWTS for sewage treatment may provide effluent of higher quality suitable for surface disposal. However on the whole, after a 1-3 m of travel through the subsurface, it was not possible to distinguish any significant differences in quality between those originating from septic tanks and AWTS. • In comparison with effluent quality from a conventional wastewater treatment plant, most systems were found to perform satisfactorily with regards to Total Nitrogen. The success rate was much lower in the case of faecal coliforms. However it is important to note that five of the systems exhibited problems with regards to effluent disposal, resulting in surface flow. This could lead to possible contamination of surface water courses. • The ratio of TDS to EC is about 0.42 whilst the optimum recommended value for use of treated effluent for irrigation should be about 0.64. This would mean a higher salt content in the effluent than what is advisable for use in irrigation. A consequence of this would be the accumulation of salts to a concentration harmful to crops or the landscape unless adequate leaching is present. These relatively high EC values are present even in the case of AWTS where surface irrigation of effluent is being undertaken. However it is important to note that this is not an artefact of the treatment process but rather an indication of the quality of the wastewater generated in the household. This clearly indicates the need for further research to evaluate the suitability of various soil types for the surface irrigation of effluent where the TDS/EC ratio is less than 0.64. • Effluent percolating through the subsurface absorption field may travel in the form of dilute pulses. As such the effluent will move through the soil profile forming fronts of elevated parameter levels. • The downward flow of effluent and leaching of the soil profile is evident in the case of podsolic, lithosol and kransozem soils. Lateral flow of effluent is evident in the case of prairie soils. Gleyed podsolic soils indicate poor drainage and ponding of effluent. In the current phase of the research project, a number of chemical indicators such as EC, pH and chloride concentration were employed as indicators to investigate the extent of effluent flow and to understand how soil renovates effluent. The soil profile, especially texture, structure and moisture regime was examined more in an engineering sense to determine the effect of movement of water into and through the soil. However it is not only the physical characteristics, but the chemical characteristics of the soil also play a key role in the effluent renovation process. Therefore in order to understand the complex processes taking place in a subsurface effluent disposal area, it is important that the identified influential parameters are evaluated using soil chemical concepts. Consequently the primary focus of the next phase of the research project will be to identify linkages between various important parameters. The research thus envisaged will help to develop robust criteria for evaluating the performance of subsurface disposal systems.

Synthesis and characterisation of layered double hydroxides and their application for water purification

Layered doubly hydroxides (LDHs) also known as hydrotalcites or anionic clays are a group of clay minerals that have shown promise for the removal of toxic anions from water through both anion exchange and a process known as the reformation effect. This project has involved the preparation and characterisation of LDH materials as well as the investigation of their ability to remove selected anions from aqueous solutions by the reformation effect. The LDH materials were successfully prepared from magnesium, aluminium, zinc and chromium chloride salts using the co-precipitation method. Samples were characterised using powder X-ray diffraction (XRD) and thermogravimetry (TG) to confirm the presence of LDHs. Powder XRD revealed a characteristic LDH structure for all LDH samples. Thermal Analysis showed decomposition usual occurred through a three or four step process as expected for LDHs. Preliminary investigations of the removal of sulfate, nitrate and fluoride by an Mg/Al LDH were carried out, and the products were characterised using XRD and TG which showed that an LDH material similar to the original hydrotalcite was formed after reformation. A Zn/Al LDH was investigated as a potential sorbent material for the removal of iodine and iodide from water. It was found that the LDH was a suitable adsorbent which is able to remove almost all of the iodine present in the test solutions. Again, the products were characterised by XRD, TG and evolved gas mass spectrometry (EGMS) in an attempt to better understand the iodine removal process. Powder XRD showed successful reformation of the LDH structure and TG/EGMS showed that only a small amount of iodine species were lost during thermal decomposition. Finally, the mineral stichtite a Mg/Cr LDH was successfully synthesised and investigated using XRD, TG and EGMS. Unfortunately, due to lack of time it was not possible to identify any new uses for the mineral stichtite in the current project.