Freshwater influences on hydrology and seagrass dynamics of intermittent estuaries

Many temperate estuaries have intermittently open and closed mouths, a feature that is often related to intermittent freshwater input. These systems, often overlooked due to their small size, can have large hydrological variability over medium-term time scales.

This variability presents potential difficulties for estuarine species particularly where anthropogenic alterations to freshwater flows can cause large deviations from natural patterns of tidal influence and inundation of habitat.

Influences of natural and hydrological variability on seagrasses were examined in two central Victorian estuaries with anthropogenically-modified but naturally-intermittent freshwater flows and mouth openings. Comparisons were focused on differences between an estuary with artificially-augmented freshwater inflow and an adjacent system, in which the volume and timing of inflows were altered by a reservoir. Eight additional estuaries in the region were also used to provide a context for these two main sites.

Hydrological changes during the three-year field component were affected by the ending of a drought and then a major flood a year later as well as by ongoing anthropogenic flow reduction and augmentation. These influences on hydrology were associated with an initially high seagrass coverage that was substantially reduced and showed signs of recovery only in the system that was affected by lower inflows. Such influences and responses also changed seasonally but to a much lesser extent than the responses to stochastic climatic events.

Natural flows were intermittent and varied substantially between years. Flooding flows represented up to 89% of the long-term annual average flow. Water quality was broadly typical of the region, with the exception of low pH in some tributaries, especially those of Anglesea estuary. Anthropogenic changes to flow were most evident at times of low natural flows and resulted in longer and more frequent periods of zero inflow to Painkalac estuary and a continual base flow to Anglesea. This base flow, from ponds containing coal ash, neutralised waters flowing from upstream and increased conductivity, except at times of high natural flow.

A three-state conceptual model of the magnitude and variability of water levels, based largely on the degree of tidal influence was identified and quantitatively assessed for the two estuaries that were the main focus of the study. These states in turn had a large influence on the area and inundation of benthic habitat. Floods tended to open the mouths of estuaries, which then remained tidal given sufficient flow to overcome sedimentary processes at the mouths. Low and zero inflow was a precondition for closure of the mouths of the estuaries. When closed, differences in inflow resulted in different endpoints in salinity patterns. From an initial pattern similar to a classic ‘salt wedge’, Painkalac estuary, with reduced inflow, quickly destratified and gradually became more saline, at times hypersaline. Anglesea estuary, with augmented flow, tended to remain stratified for longer until becoming completely fresh, given a long enough period of closure.

Episodic changes in the water quality of the estuaries were associated with different components of the freshwater flow regimes. At high flows, fresh waters of low pH with a high metal load entered Anglesea estuary. Except during the largest flood, when the estuary was completely flushed, this water was neutralised at the halocline and resulting in precipitation of metals. High flows into Painkalac were associated with elevated concentrations of clay-sourced suspended solids. During a closed period, with zero flow, a release of sediment-bound nutrients triggered by anoxia was observed in Painkalac, followed by an algal bloom.

The large decline in seagrass extent that was observed in both estuaries was closely related to floods and the subsequent reductions in potential habitat associated with the tidal states that followed. Analysis of historical patterns of extent against rainfall records suggested that periods of drought and extended mouth closures were related to establishment and expansion of beds. This model was similar to that described for South African estuaries and contrasted with more-seasonal patterns reported for local marine embayments.

Rates of in situ decomposition of seagrass detritus showed a mix of seasonal and disturbance-driven patterns of change, depending on estuary. Variability of these rates on a scale of 100s of metres was typically not significant, but there were a few episodes that were highly significant. A negative correlation between decomposition rate and seagrass extent was also observed. A novel technique for assessing cellulose decomposition potential in sediment, adapted from soil science, proved to be a useful tool for estuarine research. Results from this component of the study highlighted both small-scale variability that was inconsistent through time, and also stable differences in decomposition potential between depths and estuaries that were consistent with differences in hydrological state and salinity.

Given the relative lack of knowledge about processes in intermittent estuaries, particularly those relating to changes in freshwater inflow, results from this study will be of value both locally and for similar systems elsewhere. Locally, it is likely that flow regimes to both Anglesea and Painkalac estuaries will be reduced, following closure of the mine power station at Anglesea and due to increased demand from the reservoir above Painkalac. There is potential to manage flows from each of these sources to minimise downstream effects. Regionally, and globally, there are many intermittent estuaries in areas with Mediterranean-type climates. It has been predicted that the climates of these regions will become drier but with an increase in intensity of storm events, both of which have ramifications for flow regimes to estuaries. It is hoped that results of this study will contribute to more informed management of intermittent estuaries in the context of these likely changes.

Insight into local structure and molecular dynamics in organic solid-state ionic conductors

Elucidating the rate and geometry of molecular dynamics is particularly important for unravelling ion-conduction mechanisms in electrochemical materials. The local molecular motions in the plastic crystal 1-ethyl-1-methylpyrrolidinium tetrafluoroborate ([C2 mpyr][BF4 ]) are studied by a combination of quantum chemical calculations and advanced solid-state nuclear magnetic resonance spectroscopy. For the first time, a restricted puckering motion with a small fluctuation angle of 25° in the pyrrolidinium ring has been observed, even in the low-temperature phase (-45 °C). This local molecular motion is deemed to be particularly important for the material to maintain its plasticity, and hence, its ion mobility at low temperatures.

Modelling ion-pair geometries and dynamics in a 1-ethyl-1-methylpyrrolidinium-based ion-conductive crystal

Full conformational and energy explorations are conducted on an organic ionic plastic crystal, 1-ethyl-1-methylpyrrolidium tetrafluoroborate [C2 mpyr][BF4 ]. The onsets of various stages of dynamic behaviour, which appear to account for low-temperature solid-solid phase transitions, are investigated by using quantum-chemical simulations. It is suggested that pseudorotation of the pyrrolidine ring occurs in the first instance; the partial rotation of the entire cation subsequently occurs and may be accompanied by reorientation of the ethyl chain as the temperature increases further. A cation-anion configuration, whereby BF4 (-) interacts with the C2 mpy cation from the side of the ring, is the most likely structure in the low-temperature phase IV region. These interpretations are supported by (13) C nuclear magnetic resonance chemical-shift analysis.

Characterization of structure and energy of TixCy cluster at early formation stage in iron matrix by molecular dynamics

The structure, energy and bonding property of TixCy clusters formed in iron matrix were studied through molecular dynamics (MD) simulation method. The initial clusters with 1D-linear, 2D-ring, and 3D-tetrahedral structures were determined and their stability was calculated. The effect of temperature on the stability of the clusters was also discussed. In addition, the dissociation path of TiC clusters in iron matrix and the corresponding energy variation were analyzed. © 2014 Elsevier B.V. All rights reserved.

Solid-state NMR as a probe of anion binding: molecular dynamics and associations in a [5]polynorbornane bisurea host complexed with terephthalate

A range of solid-state NMR techniques is used to characterise a molecular host:guest complex consisting of a [5]polynorbornane bisurea host binding a terephthalate dianion guest. Detailed information is obtained on the molecular dynamics and associations from the point of view of both the host and guest molecules. The formation of the complex in the solid state is confirmed using (1)H 2D exchange NMR, and the 180° flipping of the (2)H-labelled terephthalate guest and its eventual expulsion from the complex at elevated temperatures are quantified using variable-temperature (2)H spin-echo experiments. Two-dimensional (1)H-(13)C HETCOR spectra obtained under fast magic angle spinning conditions (60 kHz) show a high resolution despite the poor crystallinity of the solid complex, and clearly reveal changes in the rigidity of the host molecule when complexed. Short-range intra- and intermolecular (1)H-(1)H proximities are also detected using 2D SQ-DQ correlation methods, providing insight into the molecular packing in the solid phase.

Avian influenza infection dynamics under variable climatic conditions, viral prevalence is rainfall driven in waterfowl from temperate, south-east Australia

Understanding Avian Influenza Virus (AIV) infection dynamics in wildlife is crucial because of possible virus spill over to livestock and humans. Studies from the northern hemisphere have suggested several ecological and environmental drivers of AIV prevalence in wild birds. To determine if the same drivers apply in the southern hemisphere, where more irregular environmental conditions prevail, we investigated AIV prevalence in ducks in relation to biotic and abiotic factors in south-eastern Australia. We sampled duck faeces for AIV and tested for an effect of bird numbers, rainfall anomaly, temperature anomaly and long-term ENSO (El-Niño Southern Oscillation) patterns on AIV prevalence. We demonstrate a positive long term effect of ENSO-related rainfall on AIV prevalence. We also found a more immediate response to rainfall where AIV prevalence was positively related to rainfall in the preceding 3-7 months. Additionally, for one duck species we found a positive relationship between their numbers and AIV prevalence, while prevalence was negatively or not affected by duck numbers in the remaining four species studied. In Australia largely non-seasonal rainfall patterns determine breeding opportunities and thereby influence bird numbers. Based on our findings we suggest that rainfall influences age structures within populations, producing an influx of immunologically naïve juveniles within the population, which may subsequently affect AIV infection dynamics. Our study suggests that drivers of AIV dynamics in the northern hemisphere do not have the same influence at our south-east Australian field site in the southern hemisphere due to more erratic climatological conditions.