Synthesis, characterisation and application of organic surfactants modified clays for water purification

This thesis offered a step forward in the development of cheap and effective materials for water treatment. It described the modification of naturally abundant clay minerals with organic molecules, and used the modified clays as effective adsorbents for the removal of recalcitrant organic water pollutants. The outcome of the study greatly extended our understanding of the synthesis and characteristic properties of clay and modified clay minerals, provided optimistic evaluation of the modified clays for environmental remediation and offered potential utility for clay minerals in the industry and environment.

Environmental applications of inorganic-organic clays for recalcitrant organic pollutants removal: Bisphenol A

Bisphenol-A (BPA) adsorption onto inorganic-organic clays (IOCs) was investigated. For this purpose, IOCs synthesised using octadecyltrimethylammonium bromide (ODTMA, organic modifier) and hydroxy aluminium (Al13, inorganic modifier) were used. Three intercalation methods were employed with varying ODTMA concentration in the synthesis of IOCs. Molecular interactions of clay surfaces with ODTMA and Al13 and their arrangements within the interlayers were determined using Fourier transform infrared spectroscopy (FTIR). Surface area and porous structure of IOCs were determined by applying Brunauer, Emmett, and Teller (BET) method to N2 adsorption-desorption isotherms. Surface area decreased upon ODTMA intercalation while it increased with Al13 pillaring. As a result, BET specific surface area of IOCs was considerably higher than those of organoclays. Initial concentration of BPA, contact time and adsorbent dose significantly affected BPA adsorption into IOCs. Pseudo-second order kinetics model is the best fit for BPA adsorption into IOCs. Both Langmuir and Freundlich adsorption isotherms were applicable for BPA adsorption (R2 > 0.91) for IOCs. Langmuir maximum adsorption capacity for IOCs was as high as 109.89 mg g‒1 and it was closely related to the loaded ODTMA amount into the clay. Hydrophobic interactions between long alkyl chains of ODTMA and BPA are responsible for BPA adsorption into IOCs.

Groundwater flow model of the Logan river alluvial aquifer system Josephville, South East Queensland

The study focuses on an alluvial plain situated within a large meander of the Logan River at Josephville near Beaudesert which supports a factory that processes gelatine. The plant draws water from on site bores, as well as the Logan River, for its production processes and produces approximately 1.5 ML per day (Douglas Partners, 2004) of waste water containing high levels of dissolved ions. At present a series of treatment ponds are used to aerate the waste water reducing the level of organic matter; the water is then used to irrigate grazing land around the site. Within the study the hydrogeology is investigated, a conceptual groundwater model is produced and a numerical groundwater flow model is developed from this. On the site are several bores that access groundwater, plus a network of monitoring bores. Assessment of drilling logs shows the area is formed from a mixture of poorly sorted Quaternary alluvial sediments with a laterally continuous aquifer comprised of coarse sands and fine gravels that is in contact with the river. This aquifer occurs at a depth of between 11 and 15 metres and is overlain by a heterogeneous mixture of silts, sands and clays. The study investigates the degree of interaction between the river and the groundwater within the fluvially derived sediments for reasons of both environmental monitoring and sustainability of the potential local groundwater resource. A conceptual hydrogeological model of the site proposes two hydrostratigraphic units, a basal aquifer of coarse-grained materials overlain by a thick semi-confining unit of finer materials. From this, a two-layer groundwater flow model and hydraulic conductivity distribution was developed based on bore monitoring and rainfall data using MODFLOW (McDonald and Harbaugh, 1988) and PEST (Doherty, 2004) based on GMS 6.5 software (EMSI, 2008). A second model was also considered with the alluvium represented as a single hydrogeological unit. Both models were calibrated to steady state conditions and sensitivity analyses of the parameters has demonstrated that both models are very stable for changes in the range of ± 10% for all parameters and still reasonably stable for changes up to ± 20% with RMS errors in the model always less that 10%. The preferred two-layer model was found to give the more realistic representation of the site, where water level variations and the numerical modeling showed that the basal layer of coarse sands and fine gravels is hydraulically connected to the river and the upper layer comprising a poorly sorted mixture of silt-rich clays and sands of very low permeability limits infiltration from the surface to the lower layer. The paucity of historical data has limited the numerical modelling to a steady state one based on groundwater levels during a drought period and forecasts for varying hydrological conditions (e.g. short term as well as prolonged dry and wet conditions) cannot reasonably be made from such a model. If future modelling is to be undertaken it is necessary to establish a regular program of groundwater monitoring and maintain a long term database of water levels to enable a transient model to be developed at a later stage. This will require a valid monitoring network to be designed with additional bores required for adequate coverage of the hydrogeological conditions at the Josephville site. Further investigations would also be enhanced by undertaking pump testing to investigate hydrogeological properties in the aquifer.

Effect of external high pressures on the clay mineral sodium montmorillonite intercalated with methylated octadecylammonium bromide surfactants

Raman microprobe spectra of the clay mineral Wyoming SWy-2-sodium montmorillonite intercalated with the surfactants, methyltrioctadecylammonium bromide (TOMA) dimethyldiotadecylammonium bromide (DODMA) and octadecyl-trimethylammonium bromide (ODTMA), have been measured in the CH2 stretching region at external pressures up to ~40 kbar with the aid of a diamond-anvil cell. In the case of the intercalated clays containing TOMA and DODMA, the Raman data afford evidence for gauche to trans conformational changes in the orientation of the CH2 chains in the surfactants with increasing pressure. These conformational changes are reversed completely upon the release of pressure.

Vibrational spectroscopic analysis of taranakite (K,NH4)Al3(PO4)3(OH) •9(H2O) from the Jenolan Caves, Australia

Many phosphate containing minerals are found in the Jenolan Caves. Such minerals are formed by the reaction of bat guano and clays from the caves. Among these cave minerals is the mineral taranakite (K,NH4)Al3(PO4)3(OH)•9(H2O) which has been identified by X-ray diffraction. Jenolan Caves taranakite has been characterised by Raman spectroscopy. Raman and infrared bands are assigned to H2PO4-, OH and NH stretching vibrations. By using a combination of XRD and Raman spectroscopy, the existence of taranakite in the caves has been proven.

A thermoanalytical assessment of an organoclay

High resolution thermogravimetric analysis (TGA) has attracted much attention in the synthesis of organoclays and its applications. In this study, organoclays were synthesised through ion exchange of a single cationic surfactant for sodium ions, and characterised by methods including X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The changes of surface properties in montmorillonite and organoclays intercalated with surfactant were determined using XRD through the changes in the basal spacing. The thermogravimetric analysis (TGA) was applied in this study to investigate more information of the configuration and structural changes in the organoclays with thermal decomposition. There are four different decompositions steps in differential thermogravimetric (DTG) curves. The obtained TG steps are relevant to the arrangement of the surfactant molecules intercalated in montmorillonite and the thermal analysis indicates the thermal stability of surfactant modified clays. This investigation provides new insights into the properties of organoclays and is important in the synthesis and processing of organoclays for environmental applications.

Identification of montgomeryite mineral [Ca4MgAl4(PO4)6.(OH)4•12H2O] found in the Jenolan Caves - Australia

In this paper, we report on many phosphate containing natural minerals found in the Jenolan Caves - Australia. Such minerals are formed by the reaction of bat guano and clays from the caves. Among these cave minerals is the montgomeryite mineral [Ca4MgAl4(PO4)6.(OH)4.12H2O]. The presence of montgomeryite in deposits of the Jenolan Caves - Australia has been identified by X-ray diffraction (XRD). Raman spectroscopy complimented with infrared spectroscopy has been used to characterize the crystal structure of montgomeryite. The Raman spectrum of a standard montgomeryite mineral is identical to that of the Jenolan Caves sample. Bands are assigned to H2PO4-, OH and NH stretching vibrations. By using a combination of XRD and Raman spectroscopy, the existence of montgomeryite in the Jenolan Caves - Australia has been proven. A mechanism for the formation of montgomeryite is proposed.

Water–rock interactions : an investigation of the relationships between mineralogy and groundwater composition and flow in a subtropical basalt aquifer

A holistic study of the composition of the basalt groundwaters of the Atherton Tablelands region in Queensland, Australia was undertaken to elucidate possible mechanisms for the evolution of these very low salinity, silica- and bicarbonate-rich groundwaters. It is proposed that aluminosilicate mineral weathering is the major contributing process to the overall composition of the basalt groundwaters. The groundwaters approach equilibrium with respect to the primary minerals with increasing pH and are mostly in equilibrium with the major secondary minerals (kaolinite and smectite), and other secondary phases such as goethite, hematite, and gibbsite, which are common accessory minerals in the Atherton basalts. The mineralogy of the basalt rocks, which has been examined using X-ray diffraction and whole rock geochemistry methods, supports the proposed model for the hydrogeochemical evolution of these groundwaters: precipitation + CO 2 (atmospheric + soil) + pyroxene + feldspars + olivine yields H 4SiO 4, HCO 3 -, Mg 2+, Na +, Ca 2+ + kaolinite and smectite clays + amorphous or crystalline silica + accessory minerals (hematite, goethite, gibbsite, carbonates, zeolites, and pyrite). The variations in the mineralogical content of these basalts also provide insights into the controls on groundwater storage and movement in this aquifer system. The fresh and weathered vesicular basalts are considered to be important in terms of zones of groundwater occurrence, while the fractures in the massive basalt are important pathways for groundwater movement.

Assessment of flood-related recharge to alluvial aquifers of an irrigated catchment following extended drought conditions using 3D visualisation and environmental tracers, Lockyer Valley, southeast Queensland, Australia.

The Lockyer Valley in southeast Queensland, Australia, hosts an economically significant alluvial aquifer system which has been impacted by prolonged drought conditions (~1997 to ~ 2009). Throughout this time, the system was under continued groundwater extraction, resulting in severe aquifer depletion. By 2008, much of the aquifer was at <30% of storage but some relief occurred with rains in early 2009. However, between December 2010 and January 2011, most of southeast Queensland experienced unprecedented flooding, which generated significant aquifer recharge. In order to understand the spatial and temporal controls of groundwater recharge in the alluvium, a detailed 3D lithological property model of gravels, sands and clays was developed using GOCAD software. The spatial distribution of recharge throughout the catchment was assessed using hydrograph data from about 400 groundwater observation wells screened at the base of the alluvium. Water levels from these bores were integrated into a catchment-wide 3D geological model using the 3D geological modelling software GOCAD; the model highlights the complexity of recharge mechanisms. To support this analysis, groundwater tracers (e.g. major and minor ions, stable isotopes, 3H and 14C) were used as independent verification. The use of these complementary methods has allowed the identification of zones where alluvial recharge primarily occurs from stream water during episodic flood events. However, the study also demonstrates that in some sections of the alluvium, rainfall recharge and discharge from the underlying basement into the alluvium are the primary recharge mechanisms of the alluvium. This is indicated by the absence of any response to the flood, as well as the observed old radiocarbon ages and distinct basement water chemistry signatures at these locations. Within the 3D geological model, integration of water chemistry and time-series displays of water level surfaces before and after the flood suggests that the spatial variations of the flood response in the alluvium are primarily controlled by the valley morphology and lithological variations within the alluvium. The integration of time-series of groundwater level surfaces in the 3D geological model also enables the quantification of the volumetric change of groundwater stored in the unconfined sections of this alluvial aquifer during drought and following flood events. The 3D representation and analysis of hydraulic and recharge information has considerable advantages over the traditional 2D approach. For example, while many studies focus on singular aspects of catchment dynamics and groundwater-surface water interactions, the 3D approach is capable of integrating multiple types of information (topography, geological, hydraulic, water chemistry and spatial) into a single representation which provides valuable insights into the major factors controlling aquifer processes.

Performance evaluation of onsite sewage treatment : results of soil investigations

Background The onsite treatment of sewage and effluent disposal is widely prevalent in rural and urban fringe areas due to the general unavailability of reticulated wastewater collection systems. Despite the low technology of the systems, failure is common and in many cases leading to adverse public health and environmental consequences. It is important therefore that careful consideration is given to the design and location of onsite sewage treatment systems. This requires an understanding of the factors that influence treatment performance. The use of subsurface absorption systems is the most common form of effluent disposal for onsite sewage treatment, particularly for septic tanks. Also, in the case of septic tanks, a subsurface disposal system is generally an integral component of the sewage treatment process. Site specific factors play a key role in the onsite treatment of sewage. The project The primary aims of the research project were: • to relate treatment performance of onsite sewage treatment systems to soil conditions at site; • to evaluate current research relating to onsite sewage treatment; and, • to identify key issues where currently there is a lack of relevant research. 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 this research project has been on septic tanks. 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. Five broad categories of soil types prevalent in the Brisbane region have been considered in this project. The number of systems investigated was based on the proportionate area of urban development within the Brisbane region located on each of the different soil types. In the initial phase of the investigation, the majority of the systems evaluated were septic tanks. However, a small number of aerobic wastewater treatment systems (AWTS) were also included. The primary aim was to compare the effluent quality of systems employing different generic treatment processes. It is important to note that the number of each different type of system investigated was relatively small. Consequently, this does not permit a statistical analysis to be undertaken of the results obtained for comparing different systems. This is an important issue considering the large number of soil physico-chemical parameters and landscape factors that can influence treatment performance and their wide variability. The report This report is the last 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 project component discussed in the current report outlines the detailed soil investigations undertaken at a selected number of sites. In the initial field sampling, a number of soil chemical properties were assessed as indicators to investigate the extent of effluent flow and to help understand what soil factors renovate the applied effluent. The soil profile attributes, especially texture, structure and moisture regime were examined more in an engineering sense to determine the effect of movement of water into and through the soil. It is important to note that it is not only the physical characteristics, but also the chemical characteristics of the soil as well as landscape factors play a key role in the effluent renovation process. In order to understand the complex processes taking place in a subsurface effluent disposal area, influential parameters were identified using soil chemical concepts. Accordingly, the primary focus of this final phase of the research project was to identify linkages between various soil chemical parameters and landscape patterns and their contribution to the effluent renovation process. The research outcomes will contribute to the development of robust criteria for evaluating the performance of subsurface effluent disposal systems. The outcomes The key findings from the soil investigations undertaken are: • Effluent renovation is primarily undertaken by a combination of various soil physico-chemical parameters and landscape factors, thereby making the effluent renovation processes strongly site dependent. • Decisions regarding site suitability for effluent disposal should not be based purely in terms of the soil type. A number of other factors such as the site location in the catena, the drainage characteristics and other physical and chemical characteristics, also exert a strong influence on site suitability. • Sites, which are difficult to characterise in terms of suitability for effluent disposal, will require a detailed soil physical and chemical analysis to be undertaken to a minimum depth of at least 1.2 m. • The Ca:Mg ratio and Exchangeable Sodium Percentage are important parameters in soil suitability assessment. A Ca:Mg ratio of less than 0.5 would generally indicate a high ESP. This in turn would mean that Na and possibly Mg are the dominant exchangeable cations, leading to probable clay dispersion. • A Ca:Mg ratio greater than 0.5 would generally indicate a low ESP in the profile, which in turn indicates increased soil stability. • In higher clay percentage soils, low ESP can have a significant effect. • The presence of high exchangeable Na can be counteracted by the presence of swelling clays, and an exchange complex co-dominated by exchangeable Ca and exchangeable Mg. This aids absorption of cations at depth, thereby reducing the likelihood of dispersion. • Salt is continually added to the soil by the effluent and problems may arise if the added salts accumulate to a concentration that is harmful to the soil structure. Under such conditions, good drainage is essential in order to allow continuous movement of water and salt through the profile. Therefore, for a site to be sustainable, it would have a maximum application rate of effluent. This would be dependent on subsurface characteristics and the surface area available for effluent disposal. • The dosing regime for effluent disposal can play a significant role in the prevention of salt accumulation in the case of poorly draining sites. Though intermittent dosing was not considered satisfactory for the removal of the clogging mat layer, it has positive attributes in the context of removal of accumulated salts in the soil.

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.

Coal seam gas waters - their geochemical signature and potential environmental implications

Coal Seam Gas (CSG) is a form of natural gas (mainly methane) sorbed in underground coal beds. To mine this gas, wells are drilled directly into an underground coal seam and groundwater (CSG water) is pumped out to the surface. This lowers the downhole piezometric pressure and enables gas desporption from the coal matrix. In the United States, this gas has been extracted commercially since the 1980s. The economic success of US CSG projects has inspired exploration and development in Australia and New Zealand. In Australia, Queensland’s Bowen and Surat basins have been the subject of increased CSG development over the last decade. CSG growth in other Australian basins has not matured to the same level but exploration and development are taking place at an accelerated pace in the Sydney Basin (Illawarra and the Hunter Valley, NSW) and in the Gunnedah Basin. Similarly, CSG exploration in New Zealand has focused in the Waikato region (Maramarua and Huntly), in the West Coast region (Buller, Reefton, and Greymouth), and in Southland (Kaitangata, Mataura, and Ohai). Figure 1 shows a Shcoeller diagram with CSG samples from selected basins in Australia, New Zealand, and the USA. CSG water from all of these basins exhibit the same geochemical signature – low calcium, low magnesium, high bicarbonate, low sulphate and, sometimes, high chloride. This water quality is a direct result of specific biological and geological processes that have taken part in the formation of CSG. In general, these processes include the weathering of rocks (carbonates, dolomite, and halite), cation exchange with clays (responsible for enhanced sodium and depleted calcium and magnesium), and biogenic processes (accounting for the presence of high bicarbonate concentrations). The salinity of CSG waters tends to be brackish (TDS < 30000 mg/l) with a fairly neutral pH. These particular characteristics need to be taken into consideration when assessing water management and disposal alternatives. Environmental issues associated with CSG water disposal have been prominent in developed basins such as the Powder River Basin (PRB) in the United States. When disposed on the land or used for irrigation, water having a high dissolved salts content may reduce water availability to crops thus affecting crop yield. In addition, the high sodium, low calcium and low magnesium concentrations increase the potential to disperse soils and significantly reduce the water infiltration rate. Therefore, CSG waters need to be properly characterised, treated, and disposed to safeguard the environment without compromising other natural resources.