Evaluation of ion exchange as a pre-treatment option for coal seam gas water

The Coal Seam Gas (CSG) industry in Australia has grown significantly in recent years. During the gas extraction process, water is also recovered which is brackish in character. In order to facilitate beneficial reuse of the water, the CSG industry has primarily invested in Reverse Osmosis (RO) as the primary method for associated water desalination. However, the presence of alkaline earth ions in the water combined with the inherent alkalinity of the water may result in RO membrane scaling. Consequently, weak acid cation (WAC) synthetic ion exchange resins were investigated as a potential solution to this potential problem. It was shown that resins were indeed highly efficient at treating single and multi-component solutions of alkaline earth ions. The interaction of the ions with the resin was found to be considerably more complex that previously reported.

Strategies for the management and treatment of coal seam gas associated water

Coal seam gas (CSG) is a growing industry in Queensland and represents a potential major employer and deliverer of financial prosperity for years to come. CSG is a natural gas composed primarily of methane and is found trapped underground in coal beds. During the gas extraction process, significant volumes of associated water are also produced. This associated water could be a valuable resource, however, the associated water comprises of various salt constituents that make it problematic for beneficial use. Consequently, there is a need to implement various water treatment strategies to purify the associated water to comply with Queensland’s strict guidelines and to mitigate environmental risks. The resultant brine is also of importance as ultimately it also has to be dealt with in an economical manner. In some ways it can be considered that the CSG industry does not face a water problem, as this has inherent value to society, but rather has a “salt issue” to solve. This study analyzes the options involved in both the water treatment and salt recovery processes. A brief overview of the constituents present in Queensland CS water is made to illustrate the challenges involved and a range of treatment technologies discussed. Water treatment technologies examined include clarification (ballasted flocculation, dissolved air flotation, electrocoagulation), membrane filtration (ultrafiltration), ion exchange softening and desalination (ion exchange, reverse osmosis desalination and capacitance deionization). In terms of brine management we highlighted reinjection, brine concentration ponds, membrane techniques (membrane distillation, forward osmosis), thermal methods, electrodialysis, electrodialysis reversal, bipolar membrane electrodialysis, wind assisted intensive evaporation, membrane crystallization, eutectic freeze crystallization and vapor compression. As an entirety this investigation is designed to be an important tool in developing CS water treatment management strategies for effective management in Queensland and worldwide.

Forward osmosis as a pre-treatment for treating coal seam gas associated water: Flux and fouling behaviours

In this study, a bench scale forward osmosis (FO) process was operated using two commonly available FO membranes in different orientations in order to examine the removal of foulants in the coal seam gas (CSG) associated water, the water flux and fouling behaviours of the process were also investigated. After 48 h of fouling simulation experiment, the water flux declined by approximately 55 and 35% of its initial level in the TFC-PRO and CTA-PRO modes (support layer facing the feed), respectively, while the flux decline in the TFC-FO and CTA-FO modes (active layer facing the feed) was insignificant. The flux decline in PRO modes was caused by the compounding effects of internal concentration polarisation and membrane fouling. However, the declined flux was completely recovered to its initial level following the hydraulic cleaning using deionised water. Dissolved organic carbon (DOC), adenosine tri-phosphate (ATP) and major inorganic scalants (Ca, Mg and silica) in the CSG feed were effectively removed by using the FO process. The results of this study suggest that the FO process shows promising potential to be employed as an effective pre-treatment for membrane purification of CSG associated water.

Particle and gaseous emissions from compressed natural gas and ultralow sulphur diesel-fuelled buses at four steady engine loads

Exhaust emissions from thirteen compressed natural gas (CNG) and nine ultralow sulphur diesel in-service transport buses were monitored on a chassis dynamometer. Measurements were carried out at idle and at three steady engine loads of 25%, 50% and 100% of maximum power at a fixed speed of 60 kmph. Emission factors were estimated for particle mass and number, carbon dioxide and oxides of nitrogen for two types of CNG buses (Scania and MAN, compatible with Euro 2 and 3 emission standards, respectively) and two types of diesel buses (Volvo Pre-Euro/Euro1 and Mercedez OC500 Euro3). All emission factors increased with load. The median particle mass emission factor for the CNG buses was less than 1% of that from the diesel buses at all loads. However, the particle number emission factors did not show a statistically significant difference between buses operating on the two types of fuel. In this paper, for the very first time, particle number emission factors are presented at four steady state engine loads for CNG buses. Median values ranged from the order of 1012 particles min-1 at idle to 1015 particles km-1 at full power. Most of the particles observed in the CNG emissions were in the nanoparticle size range and likely to be composed of volatile organic compounds The CO2 emission factors were about 20% to 30% greater for the diesel buses over the CNG buses, while the oxides of nitrogen emission factors did not show any difference due to the large variation between buses.

Membrane associated transporter protein gene (SLC45A2) and the genetic basis of normal human pigmentation variation

This work is concerned with the genetic basis of normal human pigmentation variation. Specifically, the role of polymorphisms within the solute carrier family 45 member 2 (SLC45A2 or membrane associated transporter protein; MATP) gene were investigated with respect to variation in hair, skin and eye colour ― both between and within populations. SLC45A2 is an important regulator of melanin production and mutations in the gene underly the most recently identified form of oculocutaneous albinism. There is evidence to suggest that non-synonymous polymorphisms in SLC45A2 are associated with normal pigmentation variation between populations. Therefore, the underlying hypothesis of this thesis is that polymorphisms in SLC45A2 will alter the function or regulation of the protein, thereby altering the important role it plays in melanogenesis and providing a mechanism for normal pigmentation variation. In order to investigate the role that SLC45A2 polymorphisms play in human pigmentation variation, a DNA database was established which collected pigmentation phenotypic information and blood samples of more than 700 individuals. This database was used as the foundation for two association studies outlined in this thesis, the first of which involved genotyping two previously-described non-synonymous polymorphisms, p.Glu272Lys and p.Phe374Leu, in four different population groups. For both polymorphisms, allele frequencies were significantly different between population groups and the 272Lys and 374Leu alleles were strongly associated with black hair, brown eyes and olive skin colour in Caucasians. This was the first report to show that SLC45A2 polymorphisms were associated with normal human intra-population pigmentation variation. The second association study involved genotyping several SLC45A2 promoter polymorphisms to determine if they also played a role in pigmentation variation. Firstly, the transcription start site (TSS), and hence putative proximal promoter region, was identified using 5' RNA ligase mediated rapid amplification of cDNA ends (RLM-RACE). Two alternate TSSs were identified and the putative promoter region was screened for novel polymorphisms using denaturing high performance liquid chromatography (dHPLC). A novel duplication (c.–1176_–1174dupAAT) was identified along with other previously described single nucleotide polymorphisms (c.–1721C>G and c.–1169G>A). Strong linkage disequilibrium ensured that all three polymorphisms were associated with skin colour such that the –1721G, +dup and –1169A alleles were associated with olive skin in Caucasians. No linkage disequilibrium was observed between the promoter and coding region polymorphisms, suggesting independent effects. The association analyses were complemented with functional data, showing that the –1721G, +dup and –1169A alleles significantly decreased SLC45A2 transcriptional activity. Based on in silico bioinformatic analysis that showed these alleles remove a microphthalmia-associated transcription factor (MITF) binding site, and that MITF is a known regulator of SLC45A2 (Baxter and Pavan, 2002; Du and Fisher, 2002), it was postulated that SLC45A2 promoter polymorphisms could contribute to the regulation of pigmentation by altering MITF binding affinity. Further characterisation of the SLC45A2 promoter was carried out using luciferase reporter assays to determine the transcriptional activity of different regions of the promoter. Five constructs were designed of increasing length and their promoter activity evaluated. Constitutive promoter activity was observed within the first ~200 bp and promoter activity increased as the construct size increased. The functional impact of the –1721G, +dup and –1169A alleles, which removed a MITF consensus binding site, were assessed using electrophoretic mobility shift assays (EMSA) and expression analysis of genotyped melanoblast and melanocyte cell lines. EMSA results confirmed that the promoter polymorphisms affected DNA-protein binding. Interestingly, however, the protein/s involved were not MITF, or at least MITF was not the protein directly binding to the DNA. In an effort to more thoroughly characterise the functional consequences of SLC45A2 promoter polymorphisms, the mRNA expression levels of SLC45A2 and MITF were determined in melanocyte/melanoblast cell lines. Based on SLC45A2’s role in processing and trafficking TYRP1 from the trans-Golgi network to stage 2 melanosmes, the mRNA expression of TYRP1 was also investigated. Expression results suggested a coordinated expression of pigmentation genes. This thesis has substantially contributed to the field of pigmentation by showing that SLC45A2 polymorphisms not only show allele frequency differences between population groups, but also contribute to normal pigmentation variation within a Caucasian population. In addition, promoter polymorphisms have been shown to have functional consequences for SLC45A2 transcription and the expression of other pigmentation genes. Combined, the data presented in this work supports the notion that SLC45A2 is an important contributor to normal pigmentation variation and should be the target of further research to elucidate its role in determining pigmentation phenotypes. Understanding SLC45A2’s function may lead to the development of therapeutic interventions for oculocutaneous albinism and other disorders of pigmentation. It may also help in our understanding of skin cancer susceptibility and evolutionary adaptation to different UV environments, and contribute to the forensic application of pigmentation phenotype prediction.

Expression of Potato virus Y cytoplasmic inclusion protein in tobacco results in disorganization of parenchyma cells, distortion of epidermal cells, and induces mitochondrial and chloroplast abnormalities, formation of membrane whorls and atypical lipid accumulation

Infection of plant cells by potyviruses induces the formation of cytoplasmic inclusions ranging in size from 200 to 1000 nm. To determine if the ability to form these ordered, insoluble structures is intrinsic to the potyviral cytoplasmic inclusion protein, we have expressed the cytoplasmic inclusion protein from Potato virus Y in tobacco under the control of the chrysanthemum ribulose-1,5-bisphosphate carboxylase small subunit promoter, a highly active, green tissue promoter. No cytoplasmic inclusions were observed in the leaves of transgenic tobacco using transmission electron microscopy, despite being able to clearly visualize these inclusions in Potato virus Y infected tobacco leaves under the same conditions. However, we did observe a wide range of tissue and sub-cellular abnormalities associated with the expression of the Potato virus Y cytoplasmic inclusion protein. These changes included the disruption of normal cell morphology and organization in leaves, mitochondrial and chloroplast internal reorganization, and the formation of atypical lipid accumulations. Despite these significant structural changes, however, transgenic tobacco plants were viable and the results are discussed in the context of potyviral cytoplasmic inclusion protein function.

Synthesis and characterization of sodalite–polyimide nanocomposite membranes

Nanocomposite membranes are fabricated from sodalite nanocrystals (Sod-N) dispersed in BTDA-MDA polyimide matrices and then characterized structurally and for gas separation. No voids are found upon investigation of the interfacial contact between the inorganic and organic phases, even at a Sod-N loading of up to 35 wt.%. This is due to the functionalization of the zeolite nanocrystals with amino groups (==Si_(CH3)(CH2)3NH2), which covalently link the particles to the polyimide chains in the matrices. The addition of Sod-N increases the hydrogen-gas permeability of the membranes, while nitrogen permeability decreases. Overall, these nanocomposite membranes display substantial selectivity improvements. The sodalite–polyimide membrane containing 35 wt.% Sod-N has a hydrogen permeability of 8.0 Barrers and a H2/N2 ideal selectivity of 281 at 25 C whereas the plain polyimide membrane exhibits a hydrogen permeability of 7.0 Barrers and a H2/N2 ideal selectivity of 198 at the same testing temperature.

Microstructural characterization of electron beam evaporated tungsten oxide films for gas sensing applications

Tungsten trioxide is one of the potential semiconducting materials used for sensing NH3, CO, CH4 and acetaldehyde gases. The current research aims at development, microstructural characterization and gas sensing properties of thin films of Tungsten trioxide (WO3). In this paper, we intend to present the microstructural characterization of these films as a function of post annealing heat treatment. Microstructural and elemental analysis of electron beam evaporated WO3 thin films and iron doped WO3 films (WO3:Fe) have been carried out using analytical techniques such as Transmission electron microscopy, Rutherford Backscattered Spectroscopy and XPS analysis. TEM analysis revealed that annealing at 300oC for 1 hour improves cyrstallinity of WO3 film. Both WO3 and WO3:Fe films had uniform thickness and the values corresponded to those measured during deposition. RBS results show a fairly high concentration of oxygen at the film surface as well as in the bulk for both films, which might be due to adsorption of oxygen from atmosphere or lattice oxygen vacancy inherent in WO3 structure. XPS results indicate that tungsten exists in 4d electronic state on the surface but at a depth of 10 nm, both 4d and 4f electronic states were observed. Atomic force microscopy reveals nanosize particles and porous structure of the film. This study shows e-beam evaporation technique produces nanoaparticles and porous WO3 films suitable for gas sensing applications and doping with iron decreases the porosity and particle size which can help improve the gas selectivity.

Electron beam evaporation of tungsten oxide films for gas sensors

Pure and Iron incorporated nanostructured Tungsten Oxide (WO3) thin films were investigated for gas sensing applications using noise spectroscopy. The WO3 sensor was able to detect lower concentrations (1 ppm-10 ppm) of NH3, CO, CH4 and Acetaldehyde gases at higher operating temperatures between 100oC to 250oC. The response of the WO3 sensor to NH3, CH4 and Acetaldehyde at lower temperatures (50oC-100oC) was significant when the sensor was photo-activated using blue-light emitting diode (Blue-LED). The WO3 with Fe (WO3:Fe) was found to show some response to Acetaldehyde gas only at relatively higher operating temperature (250oC) and gas concentration of 10 ppm.