Adsorption and voltammetry of butyltin compounds

The adsorption of tributyltin onto materials commonly used for the construction of sampling and analytical equipment from aqueous solutions of varying ionic composition has been examined. The adsorption appears to be controlled by non-polar interactions between tributyltin and the surface involved. Since the speciation and hence polarity of tributyltin is affected by the ionic composition of the medium, the extent of adsorption is affected by the salinity and pH of a sample. The adsorption is rapid and, unless strategies are adopted to eliminate its effects, may render analytical results invalid. The electrochemistry of tributyltin, dibutyltin and monobutyltin, individually and in mixtures, has been investigated in aqueous media at mercury electrodes. The basic electrochemistry of each compound is summarised by the reaction BunSn (4-n)+ + (4-n)e- right left harpoons BunSn where n is the number of butyl groups attached to the tin atom. However, the electrochemistry of each compound is largely confined to the surface of the mercury electrode, and the simplicity of the above reaction is disrupted by polymerisation reactions and by butyl exchange processes occurring with the mercury electrode. When mixtures of butyltin compounds are present, the various processes that occur for each individual compound interfere with each other. A direct voltaminetric method for the determination of butyltin compounds in natural waters is therefore probably not possible.

Trace metal speciation in the Pieman River catchment, western Tasmania

The Pieman River catchment has seen continuous mining of economic deposits of gold, silver, lead, copper, zinc and tin since the 1870’s. Tributaries of this river which receive mining effluent, either directly or from acid mine drainage (AMID), have total metal concentrations considerably above background levels and are of regulatory concern. The lower Pieman River is however classified as a State Reserve in which recreational fishing and tourism are the major activities. It is therefore important that water entering the lower Pieman River from upstream hydroelectric impoundments is of high quality. Metals in natural waters exist in a variety of dissolved, colloidal and particulate forms. The bioavailability and hence toxicity of heavy metal pollutants is very dependant on their physico form. Knowledge of the speciation of a metal in natural aquatic environments is therefore necessary for understanding its geochemical behaviour and biological availability. Complexation of metal ions by natural ligands in aquatic systems is believed to play a significant role in controlling their chemical speciation. This study has investigated temporal and spatial variation in complexation of metal ions in the Pieman River. The influence of pH, temperature, organic matter, salinity, ionic strength and time has been investigated in a series of field studies and in laboratory-based experiments which simulated natural and anthropogenic disturbances. Labile metals were measured using two techniques in various freshwater and estuarine environments. Diffusive gradients in thin-films (DGT) allowed in situ measurement of solution speciation whilst differential pulse anodic stripping voltammetry (DPASV) was used to measure labile metal species in water samples collected from the catchment. Organic complexation was found to be a significant regulating mechanism for copper speciation and the copper-binding ligand concentration usually exceeded the total copper concentration in the river water. Complexation was highly dependent on pH and at the river-seawater interface was also regulated by salinity, probably as a result of competitive complexation by major ions in seawater (eg. Ca 2+ ions). Zinc complexation was also evident, however total zinc concentrations in the water column often far exceeded the potential binding capacity of available ligands. In addition to organic complexation, Zn speciation may also be associated with adsorption by flocculated or resuspended colloidal Mn and/or Fe oxyhydroxides. Metal ion complexation and hence speciation was found to be highly variable within the Pieman River catchment. This presents major difficulties for environmental managers, as it is therefore not possible to make catchment-wide assumptions about the bioavailability of these metals. These results emphasise the importance of site-specific sampling protocols and speciation testing, ideally incorporating continuous, in situ monitoring.

Integrated natural resource management in Australia: the opportunity offered by a national coastal policy

Under the Australian Constitution the management (and planning) of Crown Land is a State and Territory Government responsibility. When this is considered in conjunction with the Offshore Constitutional Settlement, which affirmed that coastal waters out to three nautical miles (in general) offshore were also the responsibility of State and Territory Governments, then clearly coastal management in Australia is largely a State/Territory responsibility.

Beyond three nautical miles it is a different story. Under the United Nations Law of the Sea Convention (UNCLOS), which Australia ratified in October 1994, Australia claims jurisdiction out to 200 nautical miles and beyond (Wescott, 2000). These waters cover an area including the Antarctic claim of over 15 million square kilometres or twice the land area of Australia.

Hence in marine and coastal terms we have the national (Commonwealth) Government managing the oceans and seven State and Territory governments largely in charge of coastal management (coastal land and coastal waters). Heading "up river", State and Territory Governments plan and manage catchments.

Given the uncoordinated relationships between Australian coastal management policy and both catchment management policy and Australia's Ocean Policy (Commonwealth of Australia, 1998a and b), the Commonwealth Government's commitment to a "National Coastal Policy" presents an opportunity to progress the integration of natural resources management for the first time in decades.

Monitoring ecological impacts: concepts and practice in flowing waters

Monitoring Ecological Impacts provides the tools needed to design  assessment programs that can reliably monitor, detect and allow  management of human impacts on the natural environment. The procedures described are well-grounded in inferential logic. Step-by-step guidelines and flow diagrams provide clear and useable protocols, which are applicable to real situations.

Benthic habitat mapping in coastal waters of south–east Australia

The Victorian Marine Mapping Project will improve knowledge on the location, spatial distribution, condition and extent of marine habitats and associated biodiversity in Victorian State waters. This information will guide informed decision making, enable priority setting, and assist in targeted natural resource management planning. This project entails benthic habitat mapping over 500 square kilometers of Victorian State waters using multibeam sonar, towed video and image classification techniques. Information collected includes seafloor topography, seafloor softness and hardness (reflectivity), and information on geology and benthic flora and fauna assemblages collectively comprising habitat. Computerized semi-automated classification techniques are also being developed to provide a cost effective approach to rapid mapping and assessment of coastal habitats.

Habitat mapping is important for understanding and communicating the distribution of natural values within the marine environment. The coastal fringe of Victoria encompasses a rich and diverse ecosystem representative of coastal waters of South-east Australia. To date, extensive knowledge of these systems is limited due to the lack of available data. Knowledge of the distribution and extent of habitat is required to target management activities most effectively, and provide the basis to monitor and report on their status in the future.

Bio-economical and ethical impacts of alien finfish culture in European inland waters

Since 1989, and in comparison to the global trend, inland aquaculture production of European finfish has declined. To date, the yearly European freshwater aquaculture production is 371,727 tons, valued at over US$1 billion. Indigenous species accounted for less than one-third of the production, whereas alien species (a species that has been moved beyond its natural range of distribution) accounts for the remainder. However, in general, indigenous species command a higher market price. Currently, food quality and food safety are leading concerns of consumers, and European consumers are also becoming alert to environmentally detrimental practices. Therefore, to aim at economic sustainability, the sector needs to satisfy consumer expectations of environmentally friendly practices. It is believed that farming alien finfish species can threaten local biodiversity through escapes, and this represents a current environmental concern relative to aquaculture. In this context, an attempt is made in this paper to understand and quantify the impacts of alien finfish cultivation in European inland waters, and to suggest remedial measures.

Evaluation of the effectiveness of marine protected areas in temperate waters of Australasia

An evaluation of the effectiveness of Marine Protected Areas (MPAs) in temperate waters of Australasia has been conducted for this thesis. The aim was to identify key elements needed in a strategy for establishment and management of MPA’s in temperate waters of Australasia. This aim was achieved by assessing how effective a sample of MPA’s has been in meeting the conservation objectives for their establishment and by identifying factors that have contributed to success or failure of the MPA’s in meeting these objectives. Particular attention was paid to the objectives of ecological sustainability and biodiversity preservation. A MPA for the purposes of this research was defined as an area of coastal or marine environment, with a substantial subtidal component, set aside by law primarily for conservation purposes. The study region encompassed the coastal zones of Victoria, Tasmania and South Australia (Australia) and New Zealand. The questions posed in order to address the aim of this thesis were; a) Have existing MPA’s been effective in achieving conservation objectives? b) What have been the important influences on effectiveness of existing MPA’s? c) What are the key elements required for implementation of effective MPA’s? The thesis is divided into three parts. Part I is a review of the literature on implementation and effectiveness of MPA’s. Part II presents a detailed evaluation of one MPA: Point Lonsdale Marine Reserve (PLMR), Victoria, Australia. Part in is an evaluation of a number of Australasian temperate MPA’s based on information provided in a survey of people involved in management of MPA’s, and from a variety of published and unpublished documents. The MPA’s are described, evidence about ecological effectiveness is presented and factors that have enhanced and limited the ability of these MPA’s to achieve conservation objectives are derived. A substantial amount of scientific evidence was found for increases in abundance, mean size and size range of fish and invertebrate populations within the boundaries of ‘no-take’ MPA’s, Some evidence was found for ‘spillover’ of adults and juveniles into adjacent fishing grounds. Ecological effects detected within ‘no-take’ MPA’s in Australasia matched those described in the literature. The abundance and mean size of a number of previously exploited species have increased, migration into adjacent fishing grounds has been documented, and species richness has increased in at least one MPA. The PLMR was established primarily to protect the scientifically significant intertidal rock platforms. The results of the case study suggest that this objective has been achieved. Opinions about effectiveness were obtained for 28 MPA’s. Of these 19 were considered to be achieving some objectives and 10 were considered to be performing well in terms of overall ecological effectiveness. Positive effects on biodiversity were generally assumed as a result of reduction of damaging anthropogenic effects on habitat. Many questionnaire respondents noted an increase in community awareness about and support for marine conservation as a result of proclamation of MPA’s, Overall, the results support the value of MPA’s for sustainability of fish stocks and preservation of biodiversity, but there is substantial doubt over whether some of the MPA’s are too small to maintain benefits in the long-term. ‘No-take’ MPA’s, particularly those more remote from the impacts of human activities, have been the most effective in achieving objectives. A number of interacting factors important to eventual success of MPA’s were identified. The most important enhancing factors identified for the PLMR were physical attributes that limit the extent of human use and a strong conservation ethic amongst many of the visitors to this marine reserve. Limiting factors were far more numerous. Of most concern is the inadequacy of at-site management. Almost half of visitors to the area were not aware of its marine reserve status, despite the fact many were frequent visitors. The need for better educational and interpretative material on-site is highlighted by the results of the PLMR visitor survey. A total of 56 factors that have enhanced effectiveness and 46 factors that have limited effectiveness of Australasian temperate MPA’s were identified. A number of factors were important in more than one MPA and this was used to derive a set of critical, or key, factors. For example, a conclusion of all three approaches used in this study is that failure to implement day-to-day management through lack of resources was a major constraint on effectiveness. The importance of MPA’s to marine conservation depends, in part, on how well they are managed. The key factors that influence MPA effectiveness were used as the basis for derivation of the main requirements for implementation of MPA’s that will be capable of meeting the objectives for their establishment. The most important needs are: • that ‘no-take’ areas surrounded by buffer zones form the basis for a system of MPA’s; • that a high level of protection is bestowed by legislation and regulations; • that a minimum size be set for the ‘no-take’ core areas; • that the selection of sites for MPA’s takes into account land-based impacts; • that institutional arrangements are developed specifically for MPA’s; • that funding for MPA’s is increased to enable effective management; • that day-to-day management is implemented in all MPA’s, with enforcement and education programs as priority areas; • that a monitoring program for one or more MPA in each 'State' is established to provide evidence of ecological effects of reservation; • that public and stakeholder involvement in development and implementation of MPA’s is encouraged as this will influence the degree of public support and compliance; • that community-based programs to educate the general public, stakeholders, the media and decision-makers about the value of MPA’s are essential; and • that measures to reduce financial impact on affected stakeholders be implemented.

Removal of natural organic matter though membrane filtration and subsequent effect on disinfectant decay

This study aims to evaluate the effectiveness of membrane filtration in removing natural organic matters (NOMs) from four different source waters and the subsequent effect that it has on total chlorine (TC) demand of these waters. Source water samples were filtered sequentially through membranes with molecular weight cut-off of 3,500, 1,000 and 200 Da as well as RO membrane. The source waters and sequentially filtered samples were dosed with chlorine and the residual chlorine data were used to estimate the TC demand of these waters. A robust chlorine decay model constructed in AQUASIM software was used to do so. More than 80% of the chlorine demand in untreated surface water sources was found to be contributed mainly by NOMs that were larger than 3,500 Da. However, for water treated by granular filtration, the chlorine demand was found to be contributed by NOMs which were down to 200 Da. Sequential filtration through all four membranes reduced chlorine demand by more than 94% in surface waters and 84% in waters treated by granular filtration. Significant reduction in the formation of trihalomethane can be achieved if water is treated by appropriate membranes after granular media filtration. © 2014 © 2014 Balaban Desalination Publications. All rights reserved.

Optimization of zeaxanthin and β-carotene extraction from Chlorella saccharophila isolated from New Zealand marine waters

Zeaxanthin is an important natural pigment which has found commercial application in food and nutritional supplements. Its potential widespread use requires an easy and effective extraction methodology for obtaining higher yields. Extraction from Chlorella sp. under optimized conditions demonstrated a marked reduction in extraction time (13.48min) compared with a control experiment (30min). The extraction conditions such as solvent/cell dry weight (CDW) ratio, power, pulse, time and their combinations were optimized using response surface methodology (RSM). Almost all the variables were shown significantly (p-value <0.05) affect the carotenoid yield. Significant interaction (p-value <0.05) was observed with a substantial effect on zeaxanthin yield for solvent/CDW ratio and power, as well as power and time, whereas the β-carotene control exhibited significant interaction between solvent/CDW ratio and pulse, as well as between pulse and time. The R 2-value approached unity in both models, demonstrating their accuracy. Data obtained from these interactions were used to construct 3D response plots. Solvent/CDW ratio of 67.38μlmg-1, power 27.82% (total power 500W), pulse length of 19.7s and time 13.48min were found to be the optimized conditions for zeaxanthin (11.2mgg-1) and β-carotene (4.98mgg-1) extraction.