Дисертації з теми "Estuarine pollution"

Bramble Bay, an estuary with a long history of contamination, appears to have crossed multiple tipping points into a state of unstable biomass dominated by opportunistic species. In early 1996 mass mortality events began to affect the bay’s macrobenthic community within a few days of modest rainfall (30 mm) over the catchments. The numbers of wading birds and fish using the beach at such times greatly declined. Between mortality events the macrobenthos staged partial recoveries. However, 10 years later the beach had not attained the diversity of species it supported prior to 1996. Also, the riverine estuaries that drain the catchments had been severely affected. Monitoring in 1998 – 2000 showed that the abundance of riverine macrobenthos in six drainage systems was < 15% of that in 1972 – 1973 when these drainage systems were extensively surveyed and < 2.5% of that after extreme flooding in 1974. Remarkably, the variance of total abundance within estuaries had been reduced by 90 - 99%. Nearly all of the once-dominant peracarids had gone. Chemical tests could not explain this. Nor are other simplistic explanations credible, such as floods or changes in the rate of sedimentation, because only some components of the macrobenthos have been adversely affected. Most deposit feeders have been severely reduced, however, deposit-feeding annelids as well as suspension feeding molluscs and crustaceans have continued to thrive amongst the sediments.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
Griffith School of Environment
Science, Environment, Engineering and Technology
Full Text

The UK contains 5000 unlined historical landfills in the coastal zone currently at risk of erosion within the next 50 years. These rely on natural attenuation in surrounding sediment to reduce the contaminant load to the environment. This thesis investigates the extent and magnitude of sediment metal contamination from historical estuarine landfills. An intensive investigation of Newlands historical landfill, Essex, indicated elevated metal concentrations in surface and sub-surface sediments. Surface sediment concentrations were similar to other industrially impacted estuaries, whilst peak metal concentrations at c. 50 cm depth were indicative of industrial activity in the mid-20th Century. Below this depth, sediments were enriched with Pb (EF > 2) and Zn (EF = 1.5) indicative of an historic leachate plume that extends c. 15 m from the landfill site boundary. These sediments present a secondary source of diffuse pollution and a site contamination load of c. 1200 kg Pb. In-situ XRF was demonstrated as a rapid contamination screening tool for Fe, Pb, Sr and Zn enabling a broad-scale investigation of historical landfills across SE England. Sediment cores from eight sites containing both hazardous and inert waste were screened. Concentrations and EFs of Pb and Zn at depth were significantly higher in hazardous sites compared to inert sites. Spatial distributions of Pb and Zn were comparable to Newlands historical landfill. This indicates that diffuse pollution from historical landfill sites with similar chemical and physical attributes to Newlands is likely to present a regional, if not national problem, with UK historical landfills presenting contaminated sediments, comprising a significant, previously unidentified and unquantified diffuse pollution source in the coastal zone.

It is essential that estuarine modelling and surveying are carried out simultaneously because not only does the latter provide data required by the former but also the former is verified with data from the latter. This study integrates both research subjects from the panoramic point of view, aiming at improving modelling accuracy and reliability and increasing survey efficiency. Partially stratified estuaries are the most difficult types of estuaries to be modelled, in particular, the velocity field in such an estuary. A review of two commonly used methods to determine the velocity field, i. e., theoretical method and empirical method, revealed their inadequacies in real applications. Thus, a new approach using Kriging technique was originated and was tested on a finite element model of water quality. The model was formulated using a Galerkinfinite element method and was programmed in Fortran. Comparison between the simulation results and the field measurements for a salinity intrusion showed a high simulation accuracy. It is believed that the model in combination with the new approach would be a useful tool for estuarine modelling. The generalized Kriging method ensured that the new approach would be appropriate in practice. It was also applied to the investigation of sampling stations in the partially mixed estuary of the River Tees. It is essential to know how many sampling stations should be used and how they should be positioned. Two procedures were designed for solving the survey problems. They were the procedure of overall variance and the procedure of re-estimation. These procedures were capable of quantifing the relative significance of each sampling station and detecting redundant sampling stations. The 1975 survey was investigated, and useful conclusions were obtained.

The influence of sedimentary variables on the structure and function of infaunal estuarine and marine communities is well studied but less is known of the influence of biota on sediment properties. Feeding and burrowing activity, locomotion, the production of faecal pellets and biological secretions (bioturbation) have important implications for sediment structure, chemistry, transport characteristics and the flux of nutrients and contaminants. Although spatial and temporal patterns in bioturbation have been studied to some extent, little attention has been given to the effects of pollution. The present study examines the effects of an intertidal petrochemical discharge into the Humber estuary (UK), from BP chemicals (Saltend) Ltd on the structure and function of the communities. Field and laboratory techniques were used to determine the effects of community change on bioturbation potential. In addition, a laboratory flume was constructed to measure sediment erosion potential with field measurements being taken using a Cohesive Strength Meter (CSM). The physico-chemical properties of the sediment, changes to the infaunal community structure, bioturbation potential and the interaction of these variables were used to explain differences between the erosion potential of sediments subject to varying levels of contamination. The main study was carried out on the Saltend mudflats near Hull, with sites at various distances from the outfall being used. A further set of control sites on the adjacent, and largely unaffected, mudflat at Paull were also used. In terms of the sediment properties, sites closest to the outfall showed the greatest degree of anoxia and the highest chlorophyll-a and carbohydrate concentrations, with all three parameters being seasonally influenced. No consistent spatial or temporal patterns were found for any of the other parameters (water and organic content, particle size). Whilst the infaunal communities were characteristic of estuarine areas, macrobenthic community response followed the Pearson & Rosenberg (1978) model for organic discharges with high abundance and low species diversity being associated with the more polluted sediments. Close to the discharge, there was an impoverished community consisting predominantly of highly abundant oligochate worms. With increasing distance from the outfall, species diversity and biomass increased with Hediste diversicolor becoming increasingly dominant and the appearance of Corophium volutator, Streblospio shrubsolii and Macoma balthica. Bioturbation potential was significantly reduced (in terms of depth and burrow volume and density) by increasing effiuent concentrations and with proximity to the discharge. The diversity of both feeding and sediment modification guilds was also reduced as a result of the discharge. Both field and laboratory studies indicated a stabilising effect of this type of pollution. Using the CSM, critical shear stress values were found to be significantly lower from unpolluted sites, indicating higher erosion potential, than those from sites close to the discharge. As a result of this, the total mass of sediment eroded from unpolluted sites was significantly higher than that from polluted areas. A similar trend was observed in the laboratory with sediments treated with an effluent concentration of 32% being considerably more stable than untreated sediments. Flume studies also indicated the stabilising effect of pollution with suspended particulate matter (SPM) concentrations and mass of sediment being transported as bedload being significantly higher for unpolluted sediments. These differences in erosion potential were attributed to the direct effects of the effiuent on the physico-chemical properties of the sediment, the effects of the effiuent and sediment type on macrofaunal community structure and function and the differences in bioturbation potential between sites. The implications of these findings in the wider context of coastal management are discussed.

Mestrado em Toxicologia e Ecotoxicologia
As áreas estuarinas são geralmente focos de poluição por estarem sujeitas a uma intensa actividade antropogénica. Um exemplo disso é a poluição por tributilestanho (TBT) - um agente biocida presente nas tintas anti-incrustantes aplicadas nos cascos de embarcações. Como os estuários albergam frequentemente portos comerciais, marinas e estaleiros navais, existe aqui um intenso tráfego naval e uma elevada libertação de TBT para a água, contaminando assim todo o ambiente estuarino. Apesar da utilização do TBT em tintas anti-incrustantes de embarcações ter sido proibida em Setembro de 2008, a persistência deste composto nos sedimentos poderá causar um declínio lento dos níveis de poluição ao longo do tempo. Utilizando a Ria de Aveiro como caso de estudo, pretendeu-se neste trabalho desenvolver uma metodologia que pudesse, numa abordagem integrada, avaliar a qualidade dos sedimentos em zonas estuarinas sujeitas a intensa actividade portuária, em particular os efeitos biológicos da contaminação por TBT associada aos sedimentos. Para tal, realizaram-se campanhas de monitorização de imposex em algumas espécies de gastrópodes na Ria de Aveiro - Nassarius reticulatus e Nucella lapillus - assim como a monitorização química de TBT nos sedimentos. No laboratório foi efectuada a exposição dos gastrópodes Nassarius reticulatus e Hydrobia ulvae a sedimento colhido em alguns locais da Ria de Aveiro. Nestes bioensaios mediu-se o desenvolvimento do imposexo como resposta específica à presença de TBT nos sedimentos. Outros bioensaios foram utilizados com o objectivo de conhecer a toxicidade global dos sedimentos para outros organismos, nomeadamente, bioensaios com o gastrópode Potamopyrgus antipodarum exposto a sedimento e bioensaios com larvas do ouriço do mar, Paracentrotus lividus, expostas a “elutriados” de sedimentos. Propõe-se neste trabalho uma abordagem holística para a avaliação da poluição por TBT em zonas estuarinas, combinando a monitorização biológica (imposex), a monitorização química de TBT nos sedimentos e bioensaios laboratoriais com vista à avaliação da toxicidade dos sedimentos.
Due to intense anthropogenic activities, the estuarine areas are often outbreaks of pollution. An example is the pollution by tributyltin (TBT) - a biocide present in antifouling paints applied to boat hulls. Estuaries typically harbour commercial ports, marinas and shipyards, and consequently there is an intense naval traffic and intense release of TBT into the water, thus contaminating the entire estuarine environment. Despite the use of TBT in antifouling paints for vessels had been banned in September 2008, the persistence of this compound in sediments may cause a slow decline in pollution levels over time. Using the Ria de Aveiro as a case study, it was intended in this work to develop a methodology that could make an integrated assessment of sediment quality in estuarine areas subject to intense naval traffic, particularly the biological effects caused by the presence of TBT in sediments. To accomplish this objective, there were monitoring surveys of imposex in some species of gastropods in the Ria de Aveiro - Nassarius reticulatus and Nucella lapillus - as well as chemical monitoring of TBT in sediments. Additionally, in the laboratory, the gastropods Nassarius reticulatus and Hydrobia ulvae were exposed to sediment collected from several sites of Ria de Aveiro. These bioassays measured the development of imposex as a specific response to the presence of TBT in sediments. Other bioassays were used in order to evaluate the overall sediment toxicity to other organisms, including bioassays with the gastropod Potamopyrgus antipodarum exposed to sediment and bioassays with larvae of sea urchin, Paracentrotus lividus, exposed to sediment elutriates. It is proposed in this work a holistic approach to the assessment of pollution by TBT in estuarine areas, combining biological monitoring (imposex), chemical monitoring of TBT in sediments and laboratory bioassays for the assessment of sediment quality.

Knowledge of fine sediment delivery (both timing and loading) is fundamental to the assessment of non-point source pollution in estuarine environments. This study comprised three key components that led to the development of a fine sediment and particulate associated phosphorus budget in a typical agricultural estuary. Firstly, to explore catchment inputs, turbidity and flow were monitored continuously upstream of the freshwater/saline interface on the main stem channel of the south Devon River Avon, which drains a medium sized agricultural catchment (area 340 km2), in southwest UK. Thirty-five storms were studied in detail; and the hydrological and suspended sediment load response was observed to be highly variable. Suspended sediment concentrations (SSC) reached a maximum of 804 mg L-1 and sediment load varied from 3 to 227 t per hydrological event. Most sediment load was concentrated in winter months when competent flows occur frequently. Hydrological response was also variable in terms of lag, hydrograph shape and maximum discharge wherein the response to hydrological drivers was not consistent. Analysis of key storm parameters indicated that the hydrological response of the catchment was affected by the total amount of precipitation and antecedent rainfall history but the spatial pattern in rainfall across the catchment in relation to the spatial pattern of sediment sources was the key factor influencing total load. In the second component, examination of the sediment-associated phosphorus concentrations in the surface sediment in the Avon estuary was undertaken to evaluate spatial variation in concentration as influenced by the sediment storage dynamics of key geomorphological zones i.e. saltmarshes, intertidal flats and sandy shoals. Phosphorus concentrations ranged from 1524 to 68 mg kg-1 with higher concentrations found in saltmarsh. While there was no observed relationship between key sediment properties, particle size and total organic carbon within the different geomorphic units, a clear trend in particle size and particulate phosphorus concentration was observed longitudinally between mudflat zones linked to the sedimentation dynamics of the estuary. Furthermore, the relationship of particulate phosphorus concentration to organic matter content was modified by saltmarsh vegetation inputs to the sediment column. The final component of the work drew on evidence from a GIS and field-based survey to estimate (i) the total fine sediment and associated particulate phosphorus loading of the estuary and (ii), in conjunction with river flux data and literature evidence, the total fine sediment and PP storage and the annual sediment budget (inputs, storages and output) for the study estuary. The total amount of fine sediment stored in the estuary was ca. 99000 t which equated to 40 - 100 years of the annual sediment load of the river. Approximately 50% of all fine sediment that currently enters the estuary was estimated to be retained in storage supporting the important role of estuarine sediment sink zones in the attenuation of phosphorus. The total particulate phosphorus storage in estuary fine sediment was estimated to be 20 – 40 times the measured annual catchment particulate phosphorus input. Future changes in catchment sediment supply dynamics linked to catchment restoration programmes and soil conservation initiatives could destabilise estuarine sediment sinks and this has potentially important implications for future estuarine water quality. There is a need for further work on the potential bioavailability of estuarine sediment stored phosphorus.

Uncontrolled landfills can cause the release of significant contamination. In South England and in other parts of the UK, historical landfills are spread along the coastal and estuarine marshes and mudflats, where waste was dumped without regard to the environment. Much of the pollution from these landfills may have been dispersed and diluted into coastal waters with little impact. However, fine-grained sediments within these environments may have trapped or sequestered metals. The aim of this study is to investigate the degree to which heavy metals from these historical sites may have contaminated the adjacent marshes and intertidal mudflats.

A study of the microbial diversity in sediments of the Great Berg River estuary is carried out using modern molecular phylogenetic methods. The aim of this study was to determine the effect of (pollution by) the effluents of the fish industry on the composition of the microbial community in the sediments. The diversity in microbial groups of sediment samples that received wastewater from the local fishing industry was investigated by a PCR-DGGE (polymerase chain reaction-denaturing gradient gel electrophoresis) approach and compared to an unaffected site.

CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
O presente trabalho tem como objetivo investigar a contaminação por esgotos domésticos do sistema estuarino formado pelo rio Iguaçu e canal de Sarapuí, localizados na porção noroeste da Baía de Guanabara, através da determinação de esteróis e composição elementar (C e N) da matéria orgânica em amostras de material particulado em suspensão e sedimentos, e da caracterização físico-química e química da água e sedimento. As amostragens foram realizadas em março/2004 e setembro/2004, em 7 estações de água e 10 de sedimento, distribuídas entre 6 km a montante do rio Iguaçu e 4 km dentro da baía. Também foi coletada uma amostra composta de esgoto bruto na Estação de Tratamento da Ilha do Governador (ETIG). Na determinação dos parâmetros foram utilizados métodos analíticos já estabelecidos, tais como cromatografia a gás/espectrometria de massa (esteróis) e oxidação a seco (C e N), após otimização para as condições específicas de campo e de laboratório. As concentrações dos principais esteróis variam em escala temporal e espacial, em função de fatores climáticos e da localização de fontes difusas de esgoto. Há gradientes decrescentes de concentração de esteróis entre rio e a baía, com predomínio de esteróis fecais sobre fitoesteróis. Coprostanona (5b-colestan-3b-ona) atingindo concentrações de até 21 mg gC-1, epicolestanol (5a-colestan-5a-ol) e coprostanol (5b-colestan-3b- ol) foram os mais abundantes. A detecção de epicolestanol (inédita para a baía de Guanabara) em concentrações elevadas no material particulado e sedimento (assim como no esgoto bruto), as diferenças na composição entre esteróis no esgoto bruto em comparação com o material particulado e sedimento, e os resultados das razões entre determinados esteróis, são resultados que refletem a importância dos processos bacterianos em alterar a composição original da matéria orgânica e dos esteróis associados. O conjunto de informações levantadas confirma o elevado nível de degradação ambiental da região estudada. Por outro lado, a dinâmica do sistema e processos pré- e pós- deposicionais influenciam na geoquímica dos esteróis e, portanto, seus efeitos devem ser levados em consideração em estudos sobre marcadores moleculares em estuários com características semelhantes ao do presente trabalho.
The contamination by domestic sewage of the Iguaçu River and Sarapuí channel, located in the north-western sector of Guanabara Bay, was investigated by the determination of sterols and elemental composition (C and N) of organic matter in suspended matter and superficial sediments. Physico-chemical and chemical characterization of water and sediments were considered as well. Conventional analytical methods, like gas chromatography/mass spectrometry (sterols) and dry chemical oxidation (C and N), were employed after optimization for specific field and laboratory conditions. In March and September/2004 water/suspended particles (7 sample stations) and sediment (10 stations) were collected in a transect from 6 km up the river until 4 km off the river, in the bay. An additional sample of bulk sewage was also collected at a sewage treatment plant close to the studied area. The faecal sterols predominate over phyto sterols in suspended matter and sediments. Among the 14 sterols quantified, higher concentrations (up to 21 mg gC-1) were measured for coprostanone (5b-cholestan- 3b-one), epicholestanol (5a-cholestan-3a-ol) and coprostanol (5b-cholestan-3b- ol). In general, there is a river-bay decreasing gradient in sterol concentration, associated with the location of diffuse sources of sewage. Seasonal variation in climatic factor also influenced in the sterols distribution. The presence of epicholestanol (reported here for the first time in Guanabara Bay) in relatively high concentrations in suspended matter and sediments (as well as in raw sewage), the differences in sterol composition between raw sewage and suspended matter/sediments, and the values obtained for selected sterols source-diagnostic ratios, suggested the occurrence of significant microbial alteration of organic matter, with implications on the geochemistry of sterols. The elevated degradation

The ability to map industrial discharges through remote sensing provides a powerful tool in environmental monitoring. Radionuclide effluents have been discharged, under authorization, into the Irish Sea from BNFL (British Nuclear Fuels Plc.) sites at Sellafield and Springfields since 1952. The quantitative mapping of this anthropogenic radioactivity in estuarine intertidal zones is crucial for absolute interpretations of radionuclide transport. The spatial resolutions of traditional approaches e.g. point sampling and airborne gamma surveys are insufficient to support geomorphic interpretations of the fate of radionuclides in estuaries. The research presented in this thesis develops the use of airborne remote sensing to derive high-resolution synoptic data on the distribution of anthropogenic radionuclides in the intertidal areas of the Ribble Estuary, Lancashire, UK. From multidate surface sediment samples a significant relationship was identified between the Sellafieldderived 137Cs & 241Am and clay content (r2=0.93 & 0.84 respectively). Detailed in situ, and laboratory, reflectance (0.4-2.5mn) experiments demonstrated that significant relationships exist between Airborne Thematic Mapper (ATM) simulated reflectance and intertidal sediment grain-size. The spectral influence of moisture on the reflectance characteristics of the intertidal area is also evident. This had substantial implications for the timing of airborne image acquisition. Low-tide Daedalus ATM imagery (Natural Environmental Research Council) was collected of the Ribble Estuary on May 30th 1997. Preprocessing and linear unmixing of the imagery allowed accurate sub-pixel determinations of sediment clay content distributions (r2=0.8 1). Subsequently, the established relationships between 137Cs & 241Am and sediment grain-size enabled the radionuclide activity distributions across the entire intertidal area (92km2) to be mapped at a geomorphic scale (1.75m). The accuracy of these maps was assessed by comparison with in situ samples and the results of previous radiological studies within the estuary. Finally, detailed conclusions are made regarding radionuclide sinks and sources, and surface activity redistribution within the Ribble Estuary environment.

Estuarine acidification, caused by disturbance of acid sulfate soils (ASS), is a recurrent problem in eastern Australia. Affected waters are characterised by low pH and elevated concentrations of metals, principally aluminium and iron. The effects of acid and elevated metal concentrations associated with ASS, on adult Sydney rock oysters, have not been previously investigated. This study tested links between ASS-affected drainage, subsequent estuarine acidification and Sydney rock oyster production problems on the Hastings and Manning Rivers, mid north coast New South Wales. The primary objective of this thesis was to establish if estuarine acidification causes mortality and slow growth in individual Sydney rock oysters by exposing oysters to low pH, iron and aluminium using field and laboratory experiments. Water quality data showed that estuarine acidification was spatially extensive in the Hastings and Manning Rivers following heavy rainfall and was due to mineral acids originating from drained or excavated ASS. Estuarine acidification regularly affected areas used for Sydney rock oyster production following heavy rainfall. Field experiments showed that Sydney rock oyster mortality rates were significantly higher at sites exposed to ASS-affected waters compared to locations that were isolated from ASS-affected waters. Oyster mortality increased with the time of exposure and smaller oysters (mean weight = 5 g) experienced significantly higher mortality relative to larger oysters (mean weight = 29 g). This was caused by acid-induced shell degradation resulting in perforation of the smaller oysters??? under-developed shells. Additionally, Sydney rock oyster growth rates were dramatically reduced at sites exposed to ASS-affected waters and the overall mean condition index of oysters at ASS-affected field sites was significantly lower than the overall mean condition index of oysters at non-impacted sites. Findings from laboratory experiments showed that ASS-affected water alters oyster valve movements and significantly reduces oyster feeding rates at pH 5.5. Acidic treatments (pH 5.1) containing 7.64 mg L-1 of aluminium or ASS-affected water caused changes in the mantle and gill soft tissues following short-term exposure. Degenerative effects described in oysters in this study were also due to iron contained in ASS-affected waters. Iron precipitates accumulated on the shell, gills and mantle and were observed in the stomach, intestine, digestive tubules and rectum. This study concluded that Sydney rock oysters are unable to tolerate acidic conditions caused by ASS outflows and cannot be viably cultivated in acid-prone areas of the estuary.

Ihis work on the Sado outer estuary (western coast of Portugal) considers its bio-sedimentary characterization, and evaluates the prevailing hydrophysical and sedimentary environmental conditions. The quality status of the estuary is discussed. The thesis is based on the analysis of superficial sediments and benthic macrofauna collected from 133 sites, and on hydrodynamical data obtained from a mathematical model. The environmental variables considered were the superficial sediment temperature, granulometry and organic matter content, together with the water current velocities, flow and shear stress. The macrofaunal characterization and the analysis of the state of disturbance was based on a study of the composition, structure and spatial distribution of faunal assemblages and their relationship to the prevailing environmental conditions. The Sado was shown to be inhabited by an abundant and diversified fauna with high biomass. Two major faunal assemblages have been identified, a marine and an estuarine community, separated by a transition region. The estuarine community comprises the majority of the area and contains important subdivisions. The regions identified have been shown either to be controlled by anthropogenic inputs or to reflect mainly the effects of natural forces. The main structuring factors influencing the benthos are the hydrodynamic conditions, coupled with sediment type, and organic matter of natural and anthropogenic origin. Sedimentary organic enrichment effects have been noted in all the areas studied and in general the Sado outer estuary reveals signs of eutrophic conditions. In the more disturbed regions the macrofauna data also suggest chronic toxicity effects. Although disturbance effects due to anthropogenic inputs are suggested through the biosedimentary approach, the estuary as a whole can not be considered badly polluted. However, defaunated, impoverished and over-enriched areas, appear as a result of localised severe pollution indicating the need to improve effluent treatment systems. The methodological approach followed in this study has been shown to be effective in assessing the quality status of the Sado outer estuary. Multivariate and direct gradient analysis proved to be very useful methods and a detailed analysis of the macrofaunal species has been shown to be effective in the detection of organic enrichment effects in some of the areas. The extreme aspects of the gradients were identified by all the analytical techniques, but the univariate methods were shown to be poor at discriminating the more subtle effects.

Persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs) are widespread in aquatic systems, they can bioaccumulate in the tissues of aquatic organisms, especially fish as they occupy a position near the top of the aquatic food web. PCBs are among the most toxic substances and have been shown to cause many adverse effects to humans and wildlife. High health risks are associated with populations that follow a diet high in fat content such as fish and shellfish in which PCBs bioaccumulate. Given the importance of industries and the potential health concerns of exposure to PCBs, the lack of information on environmental levels of PCBs in South Africa (SA) is significant and concerning. Less attention has been directed to analysis of PCBs in the South African environments due to high cost and lack of appropriate equipment. This study was the first conducted in order to assess the levels of PCBs in the environment of Nelson Mandela Bay Municipality (Port Elizabeth). The research was directed at determining the PCB levels in water, sediments, fish and mussels collected in the Nelson Mandela Bay Municipality. The sampling sites, North End Lake (NEL) and Port Elizabeth Harbour (PEH) were selected based on their location and the importance of activities taking place in these areas. In total 456 samples of water (dissolved and particulate phases), sediments, mussels and tissues of fish were analysed. Suitable analytical methods were based on the equipment and materials available at the Nelson Mandela Metropolitan University. Gas chromatography-mass spectrometry (GC/MS) was used to quantify PCBs in the samples using the internal standard method. Six indicator congeners (PCB nos. 28, 52, 101, 138, 153, 180) were chosen because they are mainly present in most PCB mixtures in environmental samples and they are recommended for regular monitoring. These congeners represent about 50% of the total non-dioxin like (NDL) PCBs in food. All these congeners were detected in the samples analysed. The total PCB concentrations in the sediments from the NEL and PEH ranged from 1.60 to 3.06 and from 0.56 to 2.35 ng g-1 dry weight, respectively. The concentrations of total PCBs in Mytilus galloprovincialis ranged from 14.48 to 21.37 ng g-1 wet weight and from 20.84 to 31.34 ng g-1 wet weight in Perna perna. Total PCBs in water ranged from 0.18 to 0.355 ng L-1. The concentrations of total PCBs in the liver, gonads, gills and muscle were 95.69, 57.49, 44.63, 34.14 ng g-1 lipid weight in Cyprinus carpio and 119.73, 59.21, 49.78, 34.63 ng g-1 in Oreochromis mossambicus, respectively. Fish liver was the most contaminated organ due to its high lipid content compared to other parts of fish analysed. The NEL was found to be more contaminated than the PEH. The main potential sources of PCB pollutants in both areas of this study are industrial and municipal discharges. The NEL is surrounded by many industries and serves as a potential pollutant sink due to wastewater and inflow entering into this lake. Four 0.227 kg meals of the edible part of fish (muscle) per month were recommended based on the non-cancer health endpoint and one 0.227 kg meal per month was recommended based on the cancer health endpoint. This research contributed to notify the public and relevant governmental departments on the PCB pollution status of sediments, water and aquatic life in the PEH and NEL.

Worldwide, estuaries are under increasing pressure from numerous contaminants. There is a need to develop reliable bioassay methodologies to assess the effects of these stressors on estuary health. This thesis aimed to develop and validate toxicity tests in a New Zealand marine harpacticoid copepod species for use in monitoring and evaluating the effects of estuarine pollution. A survey and toxicological assessment of a range of native copepod species resulted in the selection of Quinquelaophonte sp. as the ideal bioassay species. This selection was based on a broad regional distribution, ease of culture and high reproductive rate in the laboratory, sexual dimorphism, and sensitivity to contaminants. To validate the bioassay, spiked sediments were used to expose Quinquelaophonte sp. to three reference compounds representing important categories of estuarine chemical stressors: zinc (a metal), atrazine (a pesticide), and phenanthrene (a polyaromatic hydrocarbon). A method for spiking sediments that Quinquelaophonte sp. inhabit was developed to ensure even contaminant distribution in sediments. Two sediment bioassays using lethal and sublethal endpoints were validated, one acute (96 h) and one chronic (14 d). These assays incorporated both lethal and sublethal endpoints, which included reproductive output and mobility. Acute-to-chronic ratios were calculated for use in environmental risk assessment and to provide insight into the mode of action of the reference contaminants. The chronic sediment bioassay was used to assess sediment quality in three estuaries across New Zealand: Napier, Christchurch and Invercargill. This validated the bioassay for use with naturally-contaminated field sediments with varying mixtures of pollutants and sediment types (coarse sandy to fine silty organic rich sediments). Quinquelaophonte sp. was also tested to assess whether it can be used to characterise multi–generation impacts. After four generations of exposure to zinc, there were changes in acute sensitivity, indicating this species possesses mechanisms for acclimating or adapting to toxic stressors. Sediment bioassays in Quinquelaophonte sp. were successfully developed and validated, offering significant promise as a tool for monitoring effects of pollution in New Zealand estuaries.

The main objective of this thesis was to study the effects of crude oil extracts on intertidal sediment communities. The approach was to focus on community structure and investigate the impact of a specific perturbation, crude oil extracts, relating to hypothetical oil spill situations. Both the impact of different disturbances on the same benthic community (i.e. with uniform structure) and the impact of the same disturbance on differently structured benthic communities were investigated. The effects on number of species, distribution of individuals between species and diversity were analysed, as well as recovery mode (trajectory of the system in time) and species arrival. The effects of different levels of a disturbance on an intertidal community were assessed, using water soluble fractions of crude oil (WSF) and two different concentrations of formaldehyde. The WSF had very little effect on community structure and recovery of the benthic community was prompt. The effects of the different concentrations of formaldehyde on the benthic community were indistinguishable: both concentrations had dramatic immediate effects. The relation between complexity and stability in benthic communities was evaluated by first setting-up two communities of different complexity using the equilibrium theory of island biogeography. After these different communities were established they were subjected to the effects of oil and dispersant. The impact of this perturbation on the two communities with different complexity was analysed both in terms of structure (as above) and functional level, through the analysis of oxygen uptake in the different communities. Although there was an indication that the oil had a depressing effect on the structure of both community types, it was not clear which species were most affected by the treatment. Individual comparisons between the two differently-structured treated communities and their controls were undertaken.

Sewage pollution from humans, animal and domestic sources (land and agricultural run-off) are recognized as a major cause of deteriorating water quality along Australia's coastline. Management of water quality has primarily relied on the use of bacterial indicator methods. However the validity and source-specificity of these methods have been met with increasing reservations for several years now. A relatively recent methodology uses a different chemical biomarker approach using 'sterols', a group of compounds related to the common bio-membrane lipid cholesterol and its derivatives. Sterols can offer an additional diagnostic tool to distinguish and discriminate between sources of faecal contamination in marine, freshwater and estuarine environments in both sediments and the water column. This study investigates for the first time, the degradation of coprostanol and selected faecal sterols in 'natural' sediments from a highly mixed (marine and estuarine) sub-tropical environment following a simulated pollution event (primary effluent); the use of faecal sterols as an additional indicator for determining non-point source sewage discharges at popular anchorages in the Moreton Bay and Gold Coast Broadwater system; and the use of sterol ratios in the determination of the fate and transportation of nutrients from a Sewage Treatment Plant (STP) point-source outlet pipe during plant malfunction. The microcosm degradation experiment revealed that faecal and selected sterols are continually synthesised and degraded over time by auto- and hetero trophic organisms within the sediment matrix. Coprostanol was the only sterol to degrade continually, with only minor fluctuations over a time period of two months. Results from this degradation experiment further revealed a sharp decline of coprostanol within the first week. From this it could be concluded that, without any further addition, external inputs of coprostanol are reduced to background levels within this time period. Therefore, removal of coprostanol after six days was 94% and 73% in mud and sand, respectively. The removal of coprostanol was much higher in mud than sand, reflecting a higher level of microbial activity in muddy sediments for assimilation of sterols. The field study undertaken at popular anchorages in Moreton Bay and the Gold Coast Broadwater revealed extremely low levels of sterols and bacterial indicators over both a spatial and temporal scale consistent with a shallow, oligotrophic, highly dynamic sand dominated system. Even though sterols analysed were found at extremely low levels (mostly in the nano-gram range), they were found to be highly correlated and were successful in identifying an unexpected once off pollution event from a point source at Moreton Bay Island. Other than this one incident, both sterol and bacterial levels were consistently low even when anchorages were at full capacity. Thus, sewage from recreational vessels was found to have very little, if any, effect on the water quality at anchorages in Moreton Bay and Gold Coast Broadwater. The point-source study conducted during a local sewage treatment plant malfunction revealed that even though absolute concentrations of sterols did not change during this event, the distribution of sterols within the samples changed, hence changing the sterol ratios. Further, nutrients (mainly nitrogen) can be transported several kilometres by currents, flocculate out of the water column and settle out into the sediment in areas with low tidal and hydrological flushing. There, the nutrients can cause in situ production of sterols in sediments changing sterol ratios. Overall, this study revealed that analyses of sterol biomarkers have the potential to indicate nutrient inputs (such as nitrogen) as well as sewage, post-hoc pollution events at extremely low levels/high dilutions in coastal sediments.

Sewage pollution from humans, animal and domestic sources (land and agricultural run-off) are recognized as a major cause of deteriorating water quality along Australia's coastline. Management of water quality has primarily relied on the use of bacterial indicator methods. However the validity and source-specificity of these methods have been met with increasing reservations for several years now. A relatively recent methodology uses a different chemical biomarker approach using 'sterols', a group of compounds related to the common bio-membrane lipid cholesterol and its derivatives. Sterols can offer an additional diagnostic tool to distinguish and discriminate between sources of faecal contamination in marine, freshwater and estuarine environments in both sediments and the water column. This study investigates for the first time, the degradation of coprostanol and selected faecal sterols in 'natural' sediments from a highly mixed (marine and estuarine) sub-tropical environment following a simulated pollution event (primary effluent); the use of faecal sterols as an additional indicator for determining non-point source sewage discharges at popular anchorages in the Moreton Bay and Gold Coast Broadwater system; and the use of sterol ratios in the determination of the fate and transportation of nutrients from a Sewage Treatment Plant (STP) point-source outlet pipe during plant malfunction. The microcosm degradation experiment revealed that faecal and selected sterols are continually synthesised and degraded over time by auto- and hetero trophic organisms within the sediment matrix. Coprostanol was the only sterol to degrade continually, with only minor fluctuations over a time period of two months. Results from this degradation experiment further revealed a sharp decline of coprostanol within the first week. From this it could be concluded that, without any further addition, external inputs of coprostanol are reduced to background levels within this time period. Therefore, removal of coprostanol after six days was 94% and 73% in mud and sand, respectively. The removal of coprostanol was much higher in mud than sand, reflecting a higher level of microbial activity in muddy sediments for assimilation of sterols. The field study undertaken at popular anchorages in Moreton Bay and the Gold Coast Broadwater revealed extremely low levels of sterols and bacterial indicators over both a spatial and temporal scale consistent with a shallow, oligotrophic, highly dynamic sand dominated system. Even though sterols analysed were found at extremely low levels (mostly in the nano-gram range), they were found to be highly correlated and were successful in identifying an unexpected once off pollution event from a point source at Moreton Bay Island. Other than this one incident, both sterol and bacterial levels were consistently low even when anchorages were at full capacity. Thus, sewage from recreational vessels was found to have very little, if any, effect on the water quality at anchorages in Moreton Bay and Gold Coast Broadwater. The point-source study conducted during a local sewage treatment plant malfunction revealed that even though absolute concentrations of sterols did not change during this event, the distribution of sterols within the samples changed, hence changing the sterol ratios. Further, nutrients (mainly nitrogen) can be transported several kilometres by currents, flocculate out of the water column and settle out into the sediment in areas with low tidal and hydrological flushing. There, the nutrients can cause in situ production of sterols in sediments changing sterol ratios. Overall, this study revealed that analyses of sterol biomarkers have the potential to indicate nutrient inputs (such as nitrogen) as well as sewage, post-hoc pollution events at extremely low levels/high dilutions in coastal sediments.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Environmental and Applied Science
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Recent evidence indicates that some of California’s coastal estuaries are contaminated with the chemical 4-nonylphenol (4-NP). Tissue burdens of 4-NP detected in the intertidal arrow goby (Clevelandia ios) in California are among the highest recorded worldwide, however, it remains unknown whether these fish are impacted by this 4-NP contamination. 4-NP is an established endocrine disrupting compound with estrogenic properties that can alter reproductive function. Furthermore, evidence that estrogens can modulate iono- and osmo-regulatory function in fishes implies that estuarine fishes exposed to 4-NP may also experience an impaired ability to maintain hydromineral balance. In Chapter 1 of this research, the time course of detectable xenoestrogen biomarker responses including gene transcripts encoding vitellogenins (vtgA and vtgC), choriogenins (chgL and chgHm), and estrogen receptors esr1 and esr2a were examined using quantitative real-time reverse transcription PCR (qRT-PCR) in adult male arrow gobies exposed to either 4-NP or E2. Specifically, adult gobies were treated with 4-NP at 10 μg/L (low 4-NP dose), or 4-NP at 100 μg/L (high 4-NP dose), ethanol vehicle (negative control), or 17β-estradiol (E2) at 50 ng/L (positive control) for 21 days. This 21 day exposure period was following by a 21 day depuration period to assess the time pattern of biomarker recovery. Results from these experiments indicated that 4-NP can induce increases in relative mRNA levels encoding vitellogenins, choriogenins, and estrogen receptor esr1 – but not esr2a – in the liver within 72 hrs, and that these transcriptional changes return to pre-exposure levels within 12 days of the termination of 4-NP or E2 exposure. In sum, these findings validate the use of mRNA levels for several estrogen-responsive genes as accurate biomarkers for short-term 4-NP exposure in the arrow goby. In Chapter 2, I evaluated the effects of 4-NP and E2 exposures on the osmoregulatory ability of C. ios. I exposed adult arrow gobies to 4-NP (10 μg/L or 100 μg/L) or E2 (50 ng/L) for 14 days, and then transferred the fish from a 33 ppt salinity (control) environment to either 20 ppt, or 5 ppt conditions. Whole body water content was then measured, and the relative mRNA levels for the ion channels Na+/K+/2Cl--cotransporter1 (nkcc1) and Na+/H+ exchanger-3 (nhe3), and the aquaporin water channel aquaporin-3 (aqp3) were quantified in the gill epithelium by qRT-PCR. Results showed that fish treated with 4-NP exhibited higher whole body water content, suggesting that 4-NP exposure results in excessive water uptake during hypoosmotic challenge. 4-NP treated gobies also exhibited elevated nkcc1 and reduced nhe3 and aqp3 mRNAs in the gill even prior to transfer of fish from the 33 ppt acclimation salinity. At 6 hrs after salinity transfer, transcripts encoding nkcc1 remained elevated in the gill epithelium of 4-NP treated gobies transferred to 20 ppt or maintained at 33 ppt (salinity control), while nhe3 and aqp3 mRNAs were still less abundant in gills of these fish. These findings point to impaired maintenance of water balance in gobies exposed to 4-NP, with those changes in fluid homeostasis possibly mediated in part by changes in gill ionic regulation. Taken as a entirety, the findings provided by this research reinforces accumulating data showing the potential for 4-NP to disrupt reproductive physiology in vertebrates, and points to the possibility that 4-NP may impair the ability of fish to regulate ion and water balance under changing salinity conditions.

Three approaches were employed to examine the effects of elevated sediment trace metal concentrations on estuarine/marine macrobenthic invertebrate assemblages. The initial study examined macroinvertebrate communities along a known polymetallic gradient, Lake Macquarie, NSW (gradient study). The second study experimentally tested if sediments sourced from different locations within Lake Macquarie differentially influenced the recolonisation of benthic invertebrates. The third study investigated the different recolonisation patterns of benthic invertebrates into sediments spiked with increasing concentrations of sediment-bound cadmium. In the Lake Macquarie gradient study, four locations (Cockle Bay, Warner's Bay, Kooroora Bay and Nord's Wharf) were sampled in winter 2000 and summer 2003 using a hierarchical design (location > site > plot). On both sampling occasions, the sediments showed strong gradients in lead, cadmium and zinc concentrations emanating from the Cockle Bay industrialised region in the lake's north, with concentrations being significantly lower in the most southern and less urbanised location (Nord's Wharf). In general, concentrations of lead, cadmium and zinc in the sediments increased among locations in the following order: Nord's Wharf > Kooroora Bay > Warner's Bay > Cockle Bay. AVSJSEM analyses indicated that in some sites in Cockle Bay, and to a lesser extent Warner's Bay, SEM concentrations exceeded their molar equivalence of AVS, indicating the potential for trace metals to be labile within the porewaters. Granulometry also changed along the gradient, with a higher proportion of silt/clay occurring in the locations with high metal concentrations. Conversely, the percentage of total organic carbon was higher in the less contaminated locations. In winter 2000, changes in benthic communities along the gradient supported the a priori hypotheses, with diversity and richness being greater in locations with lower concentrations of metals. Polychaetes were most numerous in Cockle Bay and Warner's Bay, whilst bivalves and gastropods were more abundant in Nord's Wharf and Kooroora Bay. Crustaceans were more numerous in Nord's Wharf; with all other locations having similar, lower, abundances. Ordination maps of the assemblages provided relatively clear separation of the assemblages among locations, with nonparametric multivariate analysis of variance (NPMANOVA) and subsequent pair-wise comparisons finding significant differences among the assemblages from all locations. SIMPER analyses found the highest level of dissimilarity was between the Nord's Wharf and Cockle Bay assemblages - primarily attributable to differences in the relative contributions of isopods; tellenid bivalves; and the polychaete families Spionidae, Opheliidae and Nephytidae. Weighted Spearman rank correlations (BIOENV) identified cadmium (Pw =0.74) as the strongest environmental (single or combination) variable to correlate with biotic assemblages. Benthic patterns along the gradient were less defined in summer 2003 due to a dramatic reduction in the abundance and diversity of fauna in Nord's Wharf. This decline was possibly attributable to a sustained reduction in salinity caused by a prolonged rainfall event. With the exception of Nord's Wharf, trends in the community indices and abundances of key taxa among the other locations were similar to those reported in winter 2000. Multivariate analyses discriminated the benthic assemblages from the four locations, with the findings from the NPMANOVA pair-wise comparisons indicating that the assemblages from all four locations were significantly different. SIMPER analyses showed the highest level of dissimilarity was between Nord's Wharf and Warner's Bay, with these differences being primarily attributable to their relative abundances of amphipods and polychaetes from the families Spionidae, Cirratulidae, Opheliidae and Capitellidae. BIOENV found that the combination of the sedimentary concentrations of cadmium and iron provided the best correlation (Pw =0.73) with biotic patterns, with similar correlations occumng with the addition of lead and its covariate, zinc (Pw =0.72). The combined findings from the gradient study established a strong correlation between trace metal concentrations within the sediments and suite of univariate and multivariate measurements. The low abundance and diversity of fauna in Nord's Wharf in the summer of 2003 highlighted the dynamic changes which can occur in the distributions of macrobenthic invertebrates. Although the study indicated that there was a strong relationship between trace metal concentrations and benthic community structure, the study was correlative, and requires subsequent experimental testing to confirm the causality of the observed relationships. The second component of the research was a translocation experiment using benthic recolonisation as an end-point. The experiment was performed to identify if the sediments, and not location, were influencing the composition of benthic assemblages in Lake Macquarie. Sediments were collected from three locations (Cockle Bay, Warner's Bay and Nord's Wharf), defaunated, and transplanted in three new locations along the south-east edge of the lake. At each location, 10 containers of each treatment were randomly placed in the sediment and allowed to recolonise for 22 weeks. Upon retrieval, the benthic communities were sampled and enumerated in conjunction with a variety of chemical and sedimentary measurements. Ten replicate invertebrate samples were also collected in the sediments adjacent to the experiment (ambient samples) at the completion of the experiment. Due to human interference, the containers from only two locations were analysed. Upon retrieval, pH and redox profiles of the sediments were similar to those expected in natural sediments. In general, concentrations of metals were low in the porewaters; however, iron precipitation on the porewater collection devices may have artificially increased the diffusion of metals, increasing concentrations near the sediment-water interface. Concentrations of SEM exceeded their AVS equivalence in some samples taken from the Cockle Bay and Warner's Bay treatments. Two-way ANOVAs found significant interactions between location and sediment treatments in diversity, evenness and the number of polychaetes, as well as significant differences in the number of capitellids and crustaceans among locations. Post-hoc comparisons of means found the Nord's Wharf sediment contained a higher mean number of individuals than the other treatments, including the ambient samples. nMDS ordination plots for both locations provided poor graphical discrimination of the assemblages among treatments; however, NPMANOVA detected significant location and treatment interactions. In both locations, pair-wise comparisons indicated that the assemblages within the Nord's Wharf treatments were significantly different to the Cockle Bay, Warner's Bay and ambient assemblages. No significant differences were detected between the Cockle Bay and Warner's Bay assemblages at either location. SIMPER analyses found the highest level of dissimilarity occurred between the ambient assemblages in Location 2 and the Nord's Wharf treatment, primarily due to the relative difference in the abundances of Capitellidae, Spionidae, Oweniidae, Nereididae and isopods among the assemblages. The findings from the translocation experiment suggest that the sediments are influencing the recolonisation of benthos. However, because differences were not detected between the Cockle Bay and Warner's Bay treatments, the approach used in the study shows potential as an in situ technique which could be used to assess the potential ecological risks of sediments fiom specific locations. Excluding cost and time considerations, the technique's primary disadvantage is the lack of a true control. As a result, the technique can only identify if the sediments are modifying benthic recolonisation, and not causality. The final component of the research experimentally tested if elevated concentrations of sediment-bound cadmium affected benthic invertebrate recolonisation. Sediments from the south coast of New South Wales (Durras Lake) were defaunated, and spiked with cadmium under anaerobic conditions to obtain three targeted cadmium concentrations: control (