The influence of climate variability on hydrological processes and surface and groundwater hydrochemistry : the tropical upper roper river catchment, Northern Territory, Australia

The Upper Roper River is one of the Australia’s unique tropical rivers which have been largely untouched by development. The Upper Roper River catchment comprises the sub-catchments of the Waterhouse River and Roper Creek, the two tributaries of the Roper River. There is a complex geological setting with different aquifer types. In this seasonal system, close interaction between surface water and groundwater contributes to both streamflow and sustaining ecosystems. The interaction is highly variable between seasons. A conceptual hydrogeological model was developed to investigate the different hydrological processes and geochemical parameters, and determine the baseline characteristics of water resources of this pristine catchment. In the catchment, long term average rainfall is around 850 mm and is summer dominant which significantly influences the total hydrological system. The difference between seasons is pronounced, with high rainfall up to 600 mm/month in the wet season, and negligible rainfall in the dry season. Canopy interception significantly reduces the amount of effective rainfall because of the native vegetation cover in the pristine catchment. Evaporation exceeds rainfall the majority of the year. Due to elevated evaporation and high temperature in the tropics, at least 600 mm of annual rainfall is required to generate potential recharge. Analysis of 120 years of rainfall data trend helped define “wet” and “dry periods”: decreasing trend corresponds to dry periods, and increasing trend to wet periods. The period from 1900 to 1970 was considered as Dry period 1, when there were years with no effective rainfall, and if there was, the intensity of rainfall was around 300 mm. The period 1970 – 1985 was identified as the Wet period 2, when positive effective rainfall occurred in almost every year, and the intensity reached up to 700 mm. The period 1985 – 1995 was the Dry period 2, with similar characteristics as Dry period 1. Finally, the last decade was the Wet period 2, with effective rainfall intensity up to 800 mm. This variability in rainfall over decades increased/decreased recharge and discharge, improving/reducing surface water and groundwater quantity and quality in different wet and dry periods. The stream discharge follows the rainfall pattern. In the wet season, the aquifer is replenished, groundwater levels and groundwater discharge are high, and surface runoff is the dominant component of streamflow. Waterhouse River contributes two thirds and Roper Creek one third to Roper River flow. As the dry season progresses, surface runoff depletes, and groundwater becomes the main component of stream flow. Flow in Waterhouse River is negligible, the Roper Creek dries up, but the Roper River maintains its flow throughout the year. This is due to the groundwater and spring discharge from the highly permeable Tindall Limestone and tufa aquifers. Rainfall seasonality and lithology of both the catchment and aquifers are shown to influence water chemistry. In the wet season, dilution of water bodies by rainwater is the main process. In the dry season, when groundwater provides baseflow to the streams, their chemical composition reflects lithology of the aquifers, in particular the karstic areas. Water chemistry distinguishes four types of aquifer materials described as alluvium, sandstone, limestone and tufa. Surface water in the headwaters of the Waterhouse River, the Roper Creek and their tributaries are freshwater, and reflect the alluvium and sandstone aquifers. At and downstream of the confluence of the Roper River, river water chemistry indicates the influence of rainfall dilution in the wet season, and the signature of the Tindall Limestone and tufa aquifers in the dry. Rainbow Spring on the Waterhouse River and Bitter Spring on the Little Roper River (known as Roper Creek at the headwaters) discharge from the Tindall Limestone. Botanic Walk Spring and Fig Tree Spring discharge into the Roper River from tufa. The source of water was defined based on water chemical composition of the springs, surface and groundwater. The mechanisms controlling surface water chemistry were examined to define the dominance of precipitation, evaporation or rock weathering on the water chemical composition. Simple water balance models for the catchment have been developed. The important aspects to be considered in water resource planning of this total system are the naturally high salinity in the region, especially the downstream sections, and how unpredictable climate variation may impact on the natural seasonal variability of water volumes and surface-subsurface interaction.

Three-dimensional geological modelling and multivariate statistical analysis of water chemistry data to analyse and visualise aquifer structure and groundwater composition in the Wairau Plain, Marlborough District, New Zealand

Concerns regarding groundwater contamination with nitrate and the long-term sustainability of groundwater resources have prompted the development of a multi-layered three dimensional (3D) geological model to characterise the aquifer geometry of the Wairau Plain, Marlborough District, New Zealand. The 3D geological model which consists of eight litho-stratigraphic units has been subsequently used to synthesise hydrogeological and hydrogeochemical data for different aquifers in an approach that aims to demonstrate how integration of water chemistry data within the physical framework of a 3D geological model can help to better understand and conceptualise groundwater systems in complex geological settings. Multivariate statistical techniques(e.g. Principal Component Analysis and Hierarchical Cluster Analysis) were applied to groundwater chemistry data to identify hydrochemical facies which are characteristic of distinct evolutionary pathways and a common hydrologic history of groundwaters. Principal Component Analysis on hydrochemical data demonstrated that natural water-rock interactions, redox potential and human agricultural impact are the key controls of groundwater quality in the Wairau Plain. Hierarchical Cluster Analysis revealed distinct hydrochemical water quality groups in the Wairau Plain groundwater system. Visualisation of the results of the multivariate statistical analyses and distribution of groundwater nitrate concentrations in the context of aquifer lithology highlighted the link between groundwater chemistry and the lithology of host aquifers. The methodology followed in this study can be applied in a variety of hydrogeological settings to synthesise geological, hydrogeological and hydrochemical data and present them in a format readily understood by a wide range of stakeholders. This enables a more efficient communication of the results of scientific studies to the wider community.

Understanding hydrochemical processes using 3D models and hydrochemical facies in Wairau Plain groundwater, Marlborough

Three dimensional models and groundwater quality are combined to better understand and conceptualise groundwater systems in complex geological settings in the Wairau Plain, Marlborough. Hydrochemical facies, which are characteristic of distinct evolutionary pathways and a common hydrologic history of groundwaters, are identified within geological formations to assess natural water-rock interactions, redox potential and human agricultural impact on groundwater quality in the Wairau Plain.

The role of randomly mixed-layered chlorite/smectite in the transformation of smectite to chlorite

Vesicular and groundmass phyllosilicates in a hydrothermally altered basalt from the Point Sal ophiolite, California, have been studied using transmission electron microscopy (TEM). Pore-filling phyllosilicates are texturally characterized as having coherent, relatively thick and defect-free crystals of chlorite (14 Å) with occasional 24-Å periodicities. Groundmass phyllosilicates are texturally characterized as 1) randomly oriented crystals up to 200 Å in width and 2) larger, more coherent crystals up to 1000 Å in width. Small crystallites contain predominantly 14-Å layers with some 24-Å units. Large crystals show randomly interlayered chlorite/smectite (C/S), with approximately 50% chlorite on average. Adjacent smectite-like layers are not uncommon in the groundmass phyllosilicates. Electron microprobe analyses show that Fe/Mg ratios of both groundmass and vesicular phyllosilicates are fairly constant. Termination of brucite-like interlayers has been identified in some of the TEM images. The transformation mechanisms represented by these layer terminations are 1) growth of a brucite-like interlayer within smectite interlayer regions and 2) the dissolution and reprecipitation of elements to form chlorite layers. Both mechanisms require an increase in volume as smectite transforms to chlorite. The data, combined with that from previously published reports, suggest that randomly interlayered C/S is a metastable phase formed in microenvironments with low water/rock ratios. Chlorite forms in microenvironments in the same sample dominated by higher water/rock ratios. The relatively constant number of Mg's in the structure (Mg#) of both structures indicates that in both microenvironments the bulk rock composition has influence over the composition of phyllosilicates.

Safety enhancement of water-filled road safety barrier using interaction of composite materials

Road safety barriers are used to redirect traffic at roadside work-zones. When filled with water, these barriers are able to withstand low to moderate impact speeds up to 50kmh-1. Despite this feature, Portable Water-filled barriers (PWFB) face challenges such as large lateral displacements, tearing and breakage during impact; especially at higher speeds. This study explores the use of composite action to enhance the crashworthiness of PWFBs and enable their usage at higher speeds. Initially, energy absorption capability of water in PWFB is investigated. Then, composite action of the PWFB with the introduction of steel frame is considered to evaluate its enhanced impact performance. Findings of the study show that the initial height of the impact must be lower than the free surface level of water in a PWFB in order for the water to provide significant crash energy absorption. In general, an impact of a road barrier with 80% filled is a good estimation. Furthermore, the addition of a composite structure greatly reduces the probability of tearing by decreasing the strain and impact energy transferred to the shell container. This allows the water to remain longer in the barrier to absorb energy via inertial displacements and sloshing response. Information from this research will aid in the design of new generation roadside safety structures aimed to increase safety in modern roadways.

Interaction of water with the fluorine-covered anatase TiO2(001) surface

The interaction of water with the fluorine-covered (001) surface of anatase titanium dioxide (TiO2) has been studied within the framework of density functional theory (DFT). Our results show that water dissociation is unfavorable due to repulsive interactions between surface fluorine and oxygen. We also found that the reaction of hydrofluoric acid with a surface hydroxyl group to form a surface Ti–F bond is exothermic, while the removal of fluorine from the surface needs additional energy of about half an eV. Therefore, water molecules are predicted to remain intact at the interface with the F-terminated anatase (001).

Safety enhancement of water-filled road safety barrier using interaction of composite materials

Road safety barriers are used to redirect traffic at roadside work-zones. When filled with water, these barriers are able to withstand low to moderate impact speeds up to 50kmh-1. Despite this feature, there are challenges when using portable water-filled barriers (PWFBs) such as large lateral displacements as well as tearing and breakage during impact, especially at higher speeds. In this study, the authors explore the use of composite action to enhance the crashworthiness of PWFBs and enable their use at higher speeds. Initially, we investigated the energy absorption capability of water in PWFB. Then, we considered the composite action of a PWFB with the introduction of a steel frame to evaluate its impact on performance. Findings of the study show that the initial height of impact must be lower than the free surface level of water in a PWFB for the water to provide significant crash energy absorption. In general, impact of a road barrier that is 80% filled is a good estimation. Furthermore, the addition of a composite structure greatly reduces the probability of tearing by decreasing the strain and impact energy transferred to the shell container. This allows the water to remain longer in the barrier to absorb energy via inertial displacement and sloshing response. Information from this research will aid in the design of next generation roadside safety structures aimed to increase safety on modern roadways.

Modelling water droplet movement on a leaf surface

The central aim for the research undertaken in this PhD thesis is the development of a model for simulating water droplet movement on a leaf surface and to compare the model behavior with experimental observations. A series of five papers has been presented to explain systematically the way in which this droplet modelling work has been realised. Knowing the path of the droplet on the leaf surface is important for understanding how a droplet of water, pesticide, or nutrient will be absorbed through the leaf surface. An important aspect of the research is the generation of a leaf surface representation that acts as the foundation of the droplet model. Initially a laser scanner is used to capture the surface characteristics for two types of leaves in the form of a large scattered data set. After the identification of the leaf surface boundary, a set of internal points is chosen over which a triangulation of the surface is constructed. We present a novel hybrid approach for leaf surface fitting on this triangulation that combines Clough-Tocher (CT) and radial basis function (RBF) methods to achieve a surface with a continuously turning normal. The accuracy of the hybrid technique is assessed using numerical experimentation. The hybrid CT-RBF method is shown to give good representations of Frangipani and Anthurium leaves. Such leaf models facilitate an understanding of plant development and permit the modelling of the interaction of plants with their environment. The motion of a droplet traversing this virtual leaf surface is affected by various forces including gravity, friction and resistance between the surface and the droplet. The innovation of our model is the use of thin-film theory in the context of droplet movement to determine the thickness of the droplet as it moves on the surface. Experimental verification shows that the droplet model captures reality quite well and produces realistic droplet motion on the leaf surface. Most importantly, we observed that the simulated droplet motion follows the contours of the surface and spreads as a thin film. In the future, the model may be applied to determine the path of a droplet of pesticide along a leaf surface before it falls from or comes to a standstill on the surface. It will also be used to study the paths of many droplets of water or pesticide moving and colliding on the surface.

Coal Seam Gas Water from Maramarua, New Zealand: Characterisation and Comparison to United States Analogues

Groundwater from Maramarua has been identified as coal seam gas (CSG) water by studying its composition, and comparing it against the geochemical signature from other CSG basins. CSG is natural gas that has been produced through thermogenic and biogenic processes in underground coal seams; CSG extraction requires the abstraction of significant amounts of CSG water. To date, no international literature has described coal seam gas water in New Zealand, however recent CSG exploration work has resulted in CSG water quality data from a coal seam in Maramarua, New Zealand. Water quality from this site closely follows the geochemical signature associated with United States CSG waters, and this has helped to characterise the type of water being abstracted. CSG water from this part of Maramarua has low calcium, magnesium, and sulphate concentrations but high sodium (334 mg/l), chloride (146 mg/l) and bicarbonate (435 mg/l) concentrations. In addition, this water has high pH (7.8) and alkalinity (360 mg/l as CaCO3), which is a direct consequence of carbonate dissolution and biogenic processes. Different analyte ratios ('source-rock deduction' method) have helped to identify the different formation processes responsible in shaping Maramarua CSG water

Water drinking influences eye length and IOP in young healthy subjects

This study aimed to investigate the influence of water loading upon intraocular pressure (IOP), ocular pulse amplitude (OPA) and axial length. Twenty one young adult subjects who were classified based on their spherical equivalent refraction as either myopes (n=11), or emmetropes (n=10) participated. Measures of IOP, OPA and ocular biometrics were collected before, and then 10, 15, 25 and 30 minutes following the ingestion of 1000 ml of water. Significant increases in both IOP and OPA were found to occur following water loading (p<0.0001), with peaks in both parameters occurring at 10 minutes after water loading (mean ± SEM increase of 2.24 ± 0.31 mmHg in IOP and 0.46 ± 0.06 mmHg in OPA). Axial length was found to reduce significantly following water loading (p=0.0005), with the largest reduction in axial length evident 10 minutes after water drinking (mean decrease 12 ± 3 µm). A significant time by refractive error group interaction (p=0.048) was found in axial length, indicative of a different pattern of change in eye length following water loading between the myopic and emmetropic populations. The largest difference in axial length change was evident at 10 minutes after water loading with a 17 ± 5 µm reduction in axial length evident in the myopes and only a 6 ± 2 µm reduction in the emmetropes. These findings illustrate significant changes in ocular parameters in young adult subjects following water loading.

Mechanism of interaction of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR

The development of new materials for water purification is of universal importance. Among these types of materials are layered double hydroxides (LDHs). Non-ionic materials pose a significant problem as pollutants. The interaction of methyl orange (MO) and acidic scarlet GR (GR) adsorption on hydrocalumite (Ca/Al-LDH-Cl) were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), scanning electron microscope (SEM) and near-infrared spectroscopy (NIR). The XRD results revealed that the basal spacing of Ca/Al-LDH-MO was expanded to 2.45 nm, and the MO molecules were intercalated with a inter-penetrating bilayer model in the gallery of LDH, with 49o tilting angle. Yet Ca/Al-LDH-GR was kept the same d-value as Ca/Al-LDH-Cl. The NIR spectrum for Ca/Al-LDH-MO showed a prominent band around 5994 cm-1, assigned to the combination result of the N-H stretching vibrations, which was considered as a mark to assess MO- ion intercalation into Ca/Al-LDH-Cl interlayers. From SEM images, the particle morphology of Ca/Al-LDH-MO mainly changed to irregular platelets, with a “honey-comb” like structure. Yet the Ca/Al-LDH-GR maintained regular hexagons platelets, which was similar to that of Ca/Al-LDH-Cl. All results indicated that MO- ion was intercalated into Ca/Al-LDH-Cl interlayers, and acidic scarlet GR was only adsorped upon Ca/Al-LDH-Cl surfaces.

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe - DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe 2+) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide-rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well-drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

Langevin dynamics modeling of the water diffusion tensor in partially aligned collagen networks

In this work, a Langevin dynamics model of the diffusion of water in articular cartilage was developed. Numerical simulations of the translational dynamics of water molecules and their interaction with collagen fibers were used to study the quantitative relationship between the organization of the collagen fiber network and the diffusion tensor of water in model cartilage. Langevin dynamics was used to simulate water diffusion in both ordered and partially disordered cartilage models. In addition, an analytical approach was developed to estimate the diffusion tensor for a network comprising a given distribution of fiber orientations. The key findings are that (1) an approximately linear relationship was observed between collagen volume fraction and the fractional anisotropy of the diffusion tensor in fiber networks of a given degree of alignment, (2) for any given fiber volume fraction, fractional anisotropy follows a fiber alignment dependency similar to the square of the second Legendre polynomial of cos(θ), with the minimum anisotropy occurring at approximately the magic angle (θMA), and (3) a decrease in the principal eigenvalue and an increase in the transverse eigenvalues is observed as the fiber orientation angle θ progresses from 0◦ to 90◦. The corresponding diffusion ellipsoids are prolate for θ < θMA, spherical for θ ≈ θMA, and oblate for θ > θMA. Expansion of the model to include discrimination between the combined effects of alignment disorder and collagen fiber volume fraction on the diffusion tensor is discussed.