Modelling surface and shallow groundwater interactions in an ungauged subtropical coastal catchment using the SWAT model, Elimbah Creek, southeast Queensland, Australia

The study presented here applies the highly parameterised semi-distributed U.S. Department of Agriculture Soil and Water Assessment Tool (SWAT) to an Australian subtropical catchment. SWAT has been applied to numerous catchments worldwide and is considered to be a useful tool that is under ongoing development with contributions coming from different research groups in different parts of the world. In a preliminary run the SWAT model application for the Elimbah Creek catchment has estimated water yield for the catchment and has quantified the different sources. For the modelling period of April 1999 to September 2009 the results show that the main sources of water in Elimbah Creek are total surface runoff and lateral flow (65%). Base-flow contributes 36% to the total runoff. On a seasonal basis modelling results show a shift in the source of water contributing to Elimbah Creek from surface runoff and lateral flow during intense summer storms to base-flow conditions during dry months. Further calibration and validation of these results will confirm that SWAT provides an alternative to Australian water balance models.

Image-based flow visualisation (IBFV) to enhance interpretation of complex flow patterns within a shallow tidal barrier estuary

We applied a texture-based flow visualisation technique to a numerical hydrodynamic model of the Pumicestone Passage in southeast Queensland, Australia. The quality of the visualisations using our flow visualisation tool, are compared with animations generated using more traditional drogue release plot and velocity contour and vector techniques. The texture-based method is found to be far more effective in visualising advective flow within the model domain. In some instances, it also makes it easier for the researcher to identify specific hydrodynamic features within the complex flow regimes of this shallow tidal barrier estuary as compared with the direct and geometric based methods.

Electrical imaging and fluid modeling of convective fingering in a shallow water-table aquifer

Unstable density-driven flow can lead to enhanced solute transport in groundwater. Only recently has the complex fingering pattern associated with free convection been documented in field settings. Electrical resistivity (ER) tomography has been used to capture a snapshot of convective instabilities at a single point in time, but a thorough transient analysis is still lacking in the literature. We present the results of a 2 year experimental study at a shallow aquifer in the United Arab Emirates that was designed to specifically explore the transient nature of free convection. ER tomography data documented the presence of convective fingers following a significant rainfall event. We demonstrate that the complex fingering pattern had completely disappeared a year after the rainfall event. The observation is supported by an analysis of the aquifer halite budget and hydrodynamic modeling of the transient character of the fingering instabilities. Modeling results show that the transient dynamics of the gravitational instabilities (their initial development, infiltration into the underlying lower-density groundwater, and subsequent decay) are in agreement with the timing observed in the time-lapse ER measurements. All experimental observations and modeling results are consistent with the hypothesis that a dense brine that infiltrated into the aquifer from a surficial source was the cause of free convection at this site, and that the finite nature of the dense brine source and dispersive mixing led to the decay of instabilities with time. This study highlights the importance of the transience of free convection phenomena and suggests that these processes are more rapid than was previously understood.

Synthesis, characterization and comparative study of thiophene- benzothiadiazole based donor-acceptor-donor (D-A-D) materials

The synthesis and characterization of solution processable donor-acceptor-donor (D-A-D) based conjugated molecules with varying ratios of thiophene as donor (D) and benzothiadiazole as acceptor (A) are reported. Optical, electrochemical, thermal, morphological and organic thin film transistor (OTFT) device properties of these materials were investigated. The thermal and polarized optical microscope analysis indicates that the materials having higher D/A ratios exhibit both liquid crystalline (LC) and OTFT behavior. AFM analysis of the materials having D/A ratios of 3 and 4 (3T1B and 4T1B) show well ordered structures, resulting from strong π-π interchain interactions compared to the other molecules in this study. A XRD patterns for 3T1B and 4T1B thin films also shows high crystalline ordering. Solution processed OTFTs of 3T1B and 4T1B have shown un-optimized charge carrier mobilities of 2 × 10 -2 cm 2 V -1 s -1 and 4 × 10 -3 cm 2 V -1 s -1, respectively on bare Si/SiO 2 substrate.

High mobility organic thin film transistor and efficient photovoltaic devices using versatile donor-acceptor polymer semiconductor by molecular design

In this work, we report a novel donor-acceptor based solution processable low band gap polymer semiconductor, PDPP-TNT, synthesized via Suzuki coupling using condensed diketopyrrolopyrrole (DPP) as an acceptor moiety with a fused naphthalene donor building block in the polymer backbone. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The hole mobilities of 0.65 cm2 V-1 s-1 and 0.98 cm2 V -1 s-1 are achieved respectively in bottom gate and dual gate OTFT devices with on/off ratios in the range of 105 to 10 7. Additionally, due to its appropriate HOMO (5.29 eV) energy level and optimum optical band gap (1.50 eV), PDPP-TNT is a promising candidate for organic photovoltaic (OPV) applications. When this polymer semiconductor is used as a donor and PC71BM as an acceptor in OPV devices, high power conversion efficiencies (PCE) of 4.7% are obtained. Such high mobility values in OTFTs and high PCE in OPV make PDPP-TNT a very promising polymer semiconductor for a wide range of applications in organic electronics.

Thiophene-benzothiadiazole-thiophene (D-A-D) based polymers : Effect of donor/acceptor moieties adjacent to D-A-D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

A non-fullerene electron acceptor based on fluorene and diketopyrrolopyrrole building blocks for solution-processable organic solar cells with an impressive open-circuit voltage

A novel solution-processable non-fullerene electron acceptor 6,6′-(5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP1) based on fluorene and diketopyrrolopyrrole conjugated moieties was designed, synthesized and fully characterized. DPP1 exhibited excellent solubility and high thermal stability which are essential for easy processing. Upon using DPP1 as an acceptor with the classical electron donor poly(3-hexylthiophene), solution processable bulk-heterojunction solar cells afforded a power conversion efficiency of 1.2% with a high open-circuit voltage (1.1 V). As per our knowledge, this value of open circuit voltage is one of the highest values reported so far for a bulk-heterojunction device using DPP1 as a non-fullerene acceptor.

Turbulence measurements in a shallow tidal estuary : analysis based on triple decomposition

In an estuary, mixing and dispersion are the result of the combination of large scale advection and small scale turbulence which are both complex to estimate. A field study was conducted in a small sub-tropical estuary in which high frequency (50 Hz) turbulent data were recorded continuously for about 48 hours. A triple decomposition technique was introduced to isolate the contributions of tides, resonance and turbulence in the flow field. A striking feature of the data set was the slow fluctuations which exhibited large amplitudes up to 50% the tidal amplitude under neap tide conditions. The triple decomposition technique allowed a characterisation of broader temporal scales of high frequency fluctuation data sampled during a number of full tidal cycles.

High-resolution GNSS-tracked drifter for studying surface dispersion in shallow water

The use of GNSS tracked Lagrangian drifters allows more realistic quantification of fluid motion and dispersion coefficients than Eulerian techniques because such drifters are analogues of particles that are relevant to flow field characterisation and pollutant dispersion. Using the fast growing Real Time Kinematic (RTK) positioning technique derived from Global Satellite Navigation Systems (GNSS), drifters are developed for high frequency (10 Hz) sampling with position estimates to centimetre accuracy. The drifters are designed with small size and less direct wind drag to follow the sub-surface flow which characterizes dispersion in shallow waters. An analysis of position error from stationary observation indicates that the drifter can efficiently resolve motion up to 1 Hz. The result of the field deployments of the drifter in conjunction with acoustic Eulerian devices shows higher estimate of the drifter streamwise velocities. Single particle statistical analysis of field deployments in a shallow estuarine zone yielded dispersion coefficients estimate comparable to those of dye tracer studies. The drifters capture the tidal elevation during field studies in a tidal estuary.

Integrating field survey data with satellite image data to improve shallow water seagrass maps : the role of AUV and snorkeller surveys

Repeatable and accurate seagrass mapping is required for understanding seagrass ecology and supporting management decisions. For shallow (< 5 m) seagrass habitats, these maps can be created by integrating high spatial resolution imagery with field survey data. Field survey data for seagrass is often collected via snorkelling or diving. However, these methods are limited by environmental and safety considerations. Autonomous Underwater Vehicles (AUVs) are used increasingly to collect field data for habitat mapping, albeit mostly in deeper waters (>20 m). Here we demonstrate and evaluate the use and potential advantages of AUV field data collection for calibration and validation of seagrass habitat mapping of shallow waters (< 5 m), from multispectral satellite imagery. The study was conducted in the seagrass habitats of the Eastern Banks (142 km2), Moreton Bay, Australia. In the field, georeferenced photos of the seagrass were collected along transects via snorkelling or an AUV. Photos from both collection methods were analysed manually for seagrass species composition and then used as calibration and validation data to map seagrass using an established semi-automated object based mapping routine. A comparison of the relative advantages and disadvantages of AUV and snorkeller collected field data sets and their influence on the mapping routine was conducted. AUV data collection was more consistent, repeatable and safer in comparison to snorkeller transects. Inclusion of deeper water AUV data resulted in mapping of a larger extent of seagrass (~7 km2, 5 % of study area) in the deeper waters of the site. Although overall map accuracies did not differ considerably, inclusion of the AUV data from deeper water transects corrected errors in seagrass mapped at depths to 5 m, but where the bottom is visible on satellite imagery. Our results demonstrate that further development of AUV technology is justified for the monitoring of seagrass habitats in ongoing management programs.

The origin of a large (>3km) maar volcano by coalescence of multiple shallow craters: Lake Purrumbete maar, southeastern Australia

Lake Purrumbete maar is located in the intraplate, monogenetic Newer Volcanics Province in southeastern Australia. The extremely large crater of 3000. m in diameter formed on an intersection of two fault lines and comprises at least three coalesced vents. The evolution of these vents is controlled by the interaction of the tectonic setting and the properties of both hard and soft rock aquifers. Lithics in the maar deposits originate from country rock formations less than 300. m deep, indicating that the large size of the crater cannot only be the result of the downwards migration of the explosion foci in a single vent. Vertical crater walls and primary inward dipping beds evidence that the original size of the crater has been largely preserved. Detailed mapping of the facies distributions, the direction of transport of base surges and pyroclastic flows, and the distribution of ballistic block fields, form the basis for the reconstruction of the complex eruption history,which is characterised by alternations of the eruption style between relatively dry and wet phreatomagmatic conditions, and migration of the vent location along tectonic structures. Three temporally separated eruption phases are recognised, each starting at the same crater located directly at the intersection of two local fault lines. Activity then moved quickly to different locations. A significant volcanic hiatus between two of the three phases shows that the magmatic system was reactivated. The enlargement of especially the main crater by both lateral and vertical growth led to the interception of the individual craters and the formation of the large circular crater. Lake Purrumbete maar is an excellent example of how complicated the evolution of large, seemingly simple, circular maar volcanoes can be, and raises the question if these systems are actually monogenetic.

Estimate of Lagrangian integral scales in shallow tidal water using high resolution GPS-tracked drifters

In estuaries and natural water channels, the estimate of velocity and dispersion coefficients is critical to the knowledge of scalar transport and mixing. This estimate is rarely available experimentally at sub-tidal time scale in shallow water channels where high frequency is required to capture its spatio-temporal variation. This study estimates Lagrangian integral scales and autocorrelation curves, which are key parameters for obtaining velocity fluctuations and dispersion coefficients, and their spatio-temporal variability from deployments of Lagrangian drifters sampled at 10 Hz for a 4-hour period. The power spectral densities of the velocities between 0.0001 and 0.8 Hz were well fitted with a slope of 5/3 predicted by Kolmogorov’s similarity hypothesis within the inertial subrange, and were similar to the Eulerian power spectral previously observed within the estuary. The result showed that large velocity fluctuations determine the magnitude of the integral time scale, TL. Overlapping of short segments improved the stability of the estimate of TL by taking advantage of the redundant data included in the autocorrelation function. The integral time scales were about 20 s and varied by up to a factor of 8. These results are essential inputs for spatial binning of velocities, Lagrangian stochastic modelling and single particle analysis of the tidal estuary.

Ultra-flexible nonvolatile memory based on donor-acceptor diketopyrrolopyrrole polymer blends

Flexible memory cell array based on high mobility donor-acceptor diketopyrrolopyrrole polymer has been demonstrated. The memory cell exhibits low read voltage, high cell-to-cell uniformity and good mechanical flexibility, and has reliable retention and endurance memory performance. The electrical properties of the memory devices are systematically investigated and modeled. Our results suggest that the polymer blends provide an important step towards high-density flexible nonvolatile memory devices.

Conjoint use of Dibenzosilole and Indan-1,3-dione Functionalities to Prepare an Efficient Non-Fullerene Acceptor for Solution-Processable Bulk-Heterojunction Solar Cells

A solution-processable, non-fullerene electron acceptor, 2,2′-(((5,5-dioctyl-5 H-dibenzo[b,d]silole-3,7-diyl)bis(thiophene-5,2-diyl))bis(methanylylidene))bis(1 H-indene-1,3(2 H)-dione) (called N5) comprised of dibenzosilole and 1,3-indanedione building blocks was designed, synthesized, and fully characterized. N5 is highly soluble in various organic solvents, has high thermal stability, and has energy levels matching those of archetypal donor poly(3-hexylthiophene). Solution-processable, bulk-heterojunction solar cells afforded promising power conversion efficiency of 2.76 % when N5 was used as a non-fullerene electron acceptor along with the conventional donor polymer poly(3-hexylthiophene). As per our knowledge, the material reported herein is the first example in the literature where synchronous use of such building blocks is demonstrated in the design an efficient, non-fullerene acceptor.

Crowning of dibenzosilole with a naphthalenediimide functional group to prepare an electron acceptor for organic solar cells

A novel, solution-processable non-fullerene electron acceptor 9,9′-(5,5-dioctyl-5H-dibenzo [b,d]silole-3,7-diyl)bis(2,7-dioctyl-4-(octylamino)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone) (B3) based on dibenzosilole and naphthalenediimide building blocks was designed, synthesized, characterized and successfully used in a bulk-heterojunction organic solar cell. B3 displayed excellent solubility, thermal stability and acquired electron energy levels matching with those of archetypal donor polymer poly(3-hexylthiophene). Solution-processable bulk-heterojunction devices afforded 1.16% power conversion efficiency with a high fill factor of 53%. B3 is the first example in the literature using this design principle, where mild donor units at the peripheries of end-capped naphthalenediimide units tune solubility and optical energy levels simultaneously.