Integrative catchment modelling of land use, turbidity, flow and geology

The thesis outlines and demonstrates the various aspects that contribute towards water quality management systems and the important use of storage/water quality models. The application of models is demonstrated through the functions that modelling components have on sustainable regional development, and through linkage with water quality systems.

Nonadditivity of faradaic currents and modification of double layer capacitance in the voltammetry of mixtures of ferrocene and ferrocenium salts in ionic liquids

Electrochemical studies on the Fc + e− Fc+ (Fc = ferrocene) process have been undertaken via the oxidation of Fc and reduction of Fc+ as the hexafluorophosphate (PF6−) or tetrafluoroborate (BF4−) salts and their mixtures in three ionic liquids (ILs) (1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium hexafluorophosphate). Data obtained at macro- and microdisk electrodes using conventional dc and Fourier-transformed large-amplitude ac (FT-ac) voltammetry reveal that diffusion coefficients for Fc and Fc+ differ significantly and are a function of the Fc and Fc+ concentration, in contrast to findings in molecular solvents with 0.1 M added supporting electrolyte media. Thus, the Faradaic currents associated with the oxidation of Fc (Fc0/+) and reduction of FcPF6 or FcBF4 (Fc+/0) when both Fc and Fc+ are simultaneously present in the ILs differ from values obtained when individual Fc and Fc+ solutions are used. The voltammetry for both the Fc0/+ and Fc+/0 processes exhibited near-Nernstian behavior at a glassy carbon macrodisk electrode and a platinum microdisk electrode, when each process was studied individually in the ILs. As expected, the reversible formal potentials (E°′) and diffusion coefficients (D) at 23 ± 1 °C were independent of the electrode material and concentration. However, when Fc and FcPF6 or FcBF4 were both present, alterations to the mass transport process occurred and apparent D values calculated for Fc and Fc+ were found to be about 25−39% and 32−42% larger, respectively, than those determined from individual solutions. The apparent value of the double layer capacitance determined by FT-ac voltammetry from individual and mixed Fc and Fc+ conditions at the GC electrode was also a function of concentration. Double layer capacitance values increased significantly with the concentration of Fc and FcPF6 or FcBF4 when species were studied individually or simultaneously, but had a larger magnitude under conditions where both species were present. Variation in the structure of the ILs and hence mobilities of the ionic species, when Fc and FcPF6 or FcBF4 are simultaneously present, is considered to be the origin of the nonadditivity of the Faradaic currents and variation in capacitance.

Nonadditivity of Faradaic currents and modification of capacitance currents in the voltammetry of mixtures of ferrocene and the cobaltocenium cation in protic and aprotic ionic liquids

Unexpected nonadditivity of currents encountered in the electrochemistry of mixtures of ferrocene (Fc) and cobaltocenium cation (Cc+) as the PF6 - salt has been investigated by direct current (dc) and Fourier-transformed alternating current (ac) cyclic voltammetry in two aprotic (1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate) and three protic (triethylammonium formate, bis(2-hydroxyethyl)ammonium acetate, and triethylammonium acetate) ionic liquids (ILs). The voltammetry of the individual Fc0/+ and Cc+/0 couples always exhibits near-Nernstian behavior at glassy carbon and gold electrodes. As expected for an ideal process, the reversible formal potentials and diffusion coefficients at 23 ( 1 °C in each IL determined from measurement on individual Fc and Cc+ solutions were found to be independent of electrode material, concentration, and technique used for the measurement. However, when Fc and Cc+ were simultaneously present, the dc and ac peak currents per unit concentration for the Fc0/+ and Cc+/0 processes were found to be significantly enhanced in both aprotic and protic ILs. Thus, the apparent diffusion coefficient values calculated for Fc and Cc+ were respectively found to be about 25 and 35% larger than those determined individually in the aprotic ILs. A similar change in the Fc0/+ mass transport characteristics was observed upon addition of tetrabutylammonium hexafluorophosphate (Bu4NPF6), and the double layer capacitance also varied in distinctly different ways when Fc and Cc+ were present individually or in mixtures. Importantly, the nonadditivity of Faradaic current is not associated with a change in viscosity or from electron exchange as found when some solutes are added to ILs. The observation that the 1H NMR T1 relaxation times for the proton resonance in Cc+ also are modified in mixed systems implies that specific interaction with aggregates of the constituent IL ionic species giving rise to subtle structural changes plays an important role in modifying the mass transport, double layer characteristics, and dynamics when solutes of interest in this study are added to ILs. Analogous voltammetric changes were not observed in studies in organic solvent media containing 0.1 M added supporting electrolyte. Implications of the nonadditivity of Faradaic and capacitance terms in ILs are considered.

The Bassian Isthmus and the major ocean currents of southeast Australia influence the phylogeography and population structure of a southern Australian intertidal barnacle Catomerus polymerus (Darwin)

Southern Australia is currently divided into three marine biogeographical provinces based on faunal distributions and physical parameters. These regions indicate eastern and western distributions, with an overlap occurring in the Bass Strait in Victoria. However, studies indicate that the boundaries of these provinces vary depending on the species being examined, and in particular on the mode of development employed by that species, be they direct developers or planktonic larvae dispersers. Mitochondrial DNA sequence analysis of the surf barnacle Catomerus polymerus in southern Australia revealed an east–west phylogeographical split involving two highly divergent clades (cytochrome oxidase I 3.5 ± 0.76%, control region 6.7 ± 0.65%), with almost no geographical overlap. Spatial genetic structure was not detected within either clade, indicative of a relatively long-lived planktonic larval phase. Five microsatellite loci indicated that C. polymerus populations exhibit relatively high levels of genetic divergence, and fall into four subregions: eastern Australia, central Victoria, western Victoria and Tasmania, and South Australia. F_ST values between eastern Australia (from the eastern mitochondrial DNA clade) and the remaining three subregions ranged from 0.038 to 0.159, with other analyses indicating isolation by distance between the subregions of western mitochondrial origin. We suggest that the east–west division is indicative of allopatric divergence resulting from the emergence of the Bassian land-bridge during glacial maxima, preventing gene flow between these two lineages. Subsequently, contemporary ecological conditions, namely the East Australian, Leeuwin, and Zeehan currents and the geographical disjunctions at the Coorong and Ninety Mile Beach are most likely responsible for the four subregions indicated by the microsatellite data.

Ocean currents influence the genetic structure of an intertidal mollusc in southeastern Australia – implications for predicting the movement of passive dispersers across a marine biogeographic barrier

Major disjunctions among marine communities in southeastern Australia have been well documented, although explanations for biogeographic structuring remain uncertain. Converging ocean currents, environmental gradients, and habitat discontinuities have been hypothesized as likely drivers of structuring in many species, although the extent to which species are affected appears largely dependent on specific life histories and ecologies. Understanding these relationships is critical to the management of native and invasive species, and the preservation of evolutionary processes that shape biodiversity in this region. In this study we test the direct influence of ocean currents on the genetic structure of a passive disperser across a major biogeographic barrier. Donax deltoides (Veneroida: Donacidae) is an intertidal, soft-sediment mollusc and an ideal surrogate for testing this relationship, given its lack of habitat constraints in this region, and its immense dispersal potential driven by year-long spawning and long-lived planktonic larvae. We assessed allele frequencies at 10 polymorphic microsatellite loci across 11 sample locations spanning the barrier region and identified genetic structure consistent with the major ocean currents of southeastern Australia. Analysis of mitochondrial DNA sequence data indicated no evidence of genetic structuring, but signatures of a species range expansion corresponding with historical inundations of the Bassian Isthmus. Our results indicate that ocean currents are likely to be the most influential factor affecting the genetic structure of D. deltoides and a likely physical barrier for passive dispersing marine fauna generally in southeastern Australia.

A review of long-distance movements by marine turtles, and the possible role of ocean currents

Sea turtle movements often occur in open-sea unsheltered areas, and are therefore likely to be influenced by major oceanographic processes. Only recently has work started to examine the possible relationships of these movements with dynamic oceanic features, and consequently a clear picture of such interaction is only available in a few cases. Newborn sea turtles are thought to rely on oceanic currents to reach their pelagic nursery habitats. The actual extent and timing of these developmental migrations are known for only a few populations, but these movements probably last several years and range over thousands of km. Large juveniles that have been tracked during their pelagic stage were found to make long-distance movements, sometimes swimming against the prevailing currents. Older juveniles of most species leave the pelagic habitat to recruit to neritic developmental habitats. This is a very poorly documented phase of the sea turtle life-cycle, and the few available indications show that turtles may have to swim actively for enormous distances to counterbalance their previous drift with the current. The course and extent of adult postnesting migrations vary greatly among different turtle species, but two main patterns are evident. Some species, like green, hawksbill and loggerhead turtles, shuttle between the nesting beach and a specific feeding area used for the entire inter-reproductive period. In these cases, individuals swim, rather than drift, to complete their journeys, with possible advection due to currents sometimes helping them to quickly reach their target, but sometimes providing navigational challenges. Other species such as the olive ridley and the leatherback turtle, leave the coastal nesting areas to reach the pelagic environment where they forage, and perform wandering movements. Major oceanographic processes (such as main currents and eddies) have been recently shown to have a remarkable influence on leatherback movements, making it questionable whether these journeys are to be considered migrations or, rather, prolonged stays in vast feeding areas.

Influence of ocean currents on long-distance movement of leatherback sea turtles in the Southwest Indian Ocean

Leatherback turtles Dermochelys coriacea spend most of their life in oceanic environments, whose physical and biological characteristics are primarily forged by sea current circulation. Water mass movements can mechanically act on swimming turtles, thus determining their routes, and can differentially distribute their planktonic prey. By integrating satellite tracking data with contemporaneous remote-sensing information, we analysed the post-nesting journeys of 9 leatherbacks with respect to oceanographic surface conditions. Tracked turtles showed large variations in migration routes and in final destinations, apparently without heading for specific foraging areas. Their complex tracks spread over wide regions around South Africa. Leatherbacks were greatly influenced by the currents encountered during their movements, with their trajectories displaying curves or revolutions in the presence of (and in accordance with) rotating water masses. An impressive similarity was observed between large parts of the turtle routes and those of surface drifters tracked in the same regions. Finally, leatherbacks remained associated for long periods with specific oceanographic features, which most probably offered them profitable foraging opportunities. These results agree with previous findings in showing a strong influence of oceanic currents and mesoscale features on the movements of South African leatherbacks, and additionally identify the role of current-related features in causing the observed route variability and in determining high-quality foraging hotspots for leatherbacks moving in the ocean.

A biologist's guide to assessing ocean currents : a review

We review how ocean currents are measured (in both Eulerian and Lagrangian frameworks), how they are inferred from satellite observations, and how they are simulated in ocean general circulation models (OGCMs). We then consider the value of these ‘direct’ (in situ) and ‘indirect’ (inferred, simulated) approaches to biologists investigating current-induced drift of strong-swimming vertebrates as well as dispersion of small organisms in the open ocean. We subsequently describe 2 case studies. In the first, OGCM-simulated currents were compared with satellite-derived currents; analyses suggest that the 2 methods yield similar results, but that each has its own limitations and associated uncertainty. In the second analysis, numerical methods were tested using Lagrangian drifter buoys. Results indicated that currents simulated in OGCMs do not capture all details of buoy trajectories, but do successfully resolve most general aspects of current flows. We thus recommend that the errors and uncertainties in ocean current measurements, as well as limitations in spatial and temporal resolution of the surface current data, need to be considered in tracking studies that incorporate oceanographic data. Whenever possible, cross-validation of the different methods (e.g. indirect estimates versus buoy trajectories) should be undertaken before a decision is reached about which technique is best for a specific application.

Predictive motion planning for AUVs subject to strong time-varying currents and forecasting uncertainties

This paper presents a novel path planning method for minimizing the energy consumption of an autonomous underwater vehicle subjected to time varying ocean disturbances and forecast model uncertainty. The algorithm determines 4-Dimensional path candidates using Nonlinear Robust Model Predictive Control (NRMPC) and solutions optimised using A∗-like algorithms. Vehicle performance limits are incorporated into the algorithm with disturbances represented as spatial and temporally varying ocean currents with a bounded uncertainty in their predictions. The proposed algorithm is demonstrated through simulations using a 4-Dimensional, spatially distributed time-series predictive ocean current model. Results show the combined NRMPC and A∗ approach is capable of generating energy-efficient paths which are resistant to both dynamic disturbances and ocean model uncertainty.