Rozprawy doktorskie na temat „Estuarine sediments”

The resuspension behavior of natural estuarine sediments was studied using the VIMS Sea Carousel, a benthic annular flume. The bed shear stresses produced by the flume were measured by a hot-film sensor mounted flush on the bottom of a laboratory version of the Carousel under a clear-water and flat-bottom condition. Measurements showed a reasonably uniform bed shear stress across the channel and agreed with the relationship &\tau\sb{lcub}\rm b{rcub}=0.011\Omega\sp{lcub}1.69{rcub},& where &\Omega& = ring speed (rpm) and &\tau\sb{lcub}\rm b{rcub}& = spatially-averaged bed shear stress (N/m&\sp2&), predicted from a previous numerical study. Thus, the &\tau\sb{lcub}\rm b{rcub}& was used as a bed shear stress parameter for this study. Field resuspension experiments were conducted during each season for a full year at two sites in the lower Chesapeake Bay. All the field measurements indicated the existence of surficial fluff on top of the relatively well consolidated sediment beds. These sediment beds behaved like cohesive beds despite the sand dominance, and showed an exponentially decreasing resuspension rate with time for a constant &\tau\sb{lcub}\rm b{rcub}.& These characteristics reflect that the natural sediment beds at the study sites developed a depth-increasing erosion resistance profile. Measured critical bed shear stress, &\tau\sb{lcub}\rm cr{rcub},& was slightly larger at the Wolftrap site than at the Cherrystone site (0.13 &\sim& 0.15 vs. 0.1 &\sim& 0.12 N/m&\sp2&) because of the spatial variation of physical energy condition and biological activity. The temporal variation of sediment erodibility was observed at Cherrystone, but it was not apparent at Wolftrap. From all of the field measurements, a relationship (n = 32, r&\sp2& = 0.89) was found between initial resuspension rate (E&\sb{lcub}\rm o{rcub},& in kg/m&\sp2&/sec) and approximate excess bed shear stress (&\rm\tau\sb{lcub}b{rcub}&-&\rm\tau\sb{lcub}cr{rcub},& in N/m&\sp2&), E&\sb{lcub}\rm o{rcub}& = M(&\tau\sb{lcub}\rm b{rcub}&-&\tau\sb{lcub}\rm cr{rcub})\sp\eta,& where the constants M and &\eta& are 0.018 and 1.88, respectively. Laboratory resuspension tests using the bottom sediments collected at the field sites showed a noncohesive nature of sediment bed (e.g. ripple formation) and much smaller E&\sb{lcub}o{rcub}& (&1\sim2& orders of magnitude) than those measured in the field. These differences reflect the complex nature of sediment properties and constant biophysical reworking processes in the natural environments. The differences also indicate that the direct application of the laboratory results to predict the erodibility of natural sediment is not warranted.

Orientadores: Wanilson Luiz Silva, Denis Moledo de Souza Abessa
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências
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Resumo: O sedimento representa um importante compartimento na avaliação do nível de contaminação dos ecossistemas aquáticos, pois nele é possível observar o acúmulo e a integração de muitos contaminantes presentes. O sistema estuarino de Santos-Cubatão (SP) tem sido apontado como um ambiente sedimentar seriamente poluído, devido à emissão descontrolada de efluentes urbanos e industriais. Neste sistema, o rio Morrão (foco deste estudo) tem sofrido, em particular, o impacto de atividades nos últimos 60 anos de indústria de fertilizantes e siderurgia. Com o objetivo de avaliar a qualidade dos sedimentos deste ambiente, estudos da toxicidade e biodisponibilidade de alguns contaminantes e caracterização físico-química foram realizados durante a estação seca, em amostras coletadas ao longo da borda do manguezal. Na avaliação, vários parâmetros ambientais foram levantados, incluindo: determinação de monossulfetos volatilizáveis por acidificação (AVS) e metais simultaneamente extraídos (SEM); granulometria (caracterização da textura) e matéria orgânica (MO) dos sedimentos; análise da concentração total dos elementos químicos; e aplicação de testes ecotoxicológicos agudo (utilizando-se Tiburonella viscana) e crônico (copépodes Nitocra sp). Os resultados obtidos apresentaram sedimentos com a fração silte dominante (>60% do volume das amostras) e a MO mostrou valores entre 9,15% e 22,3%. O AVS apresentou concentrações entre 0,43 e 41,38 µmol g?1 nos pontos amostrados e SEM entre 0,48 a 7,02 µmol g?1, sugerindo que efeitos adversos nos organismos expostos não seriam potencialmente esperados na área de estudo. Contudo, testes com os organismos vivos revelaram toxicidade aguda em alguns pontos, enquanto a toxicidade crônica foi evidente em todos os pontos amostrados. O método SEM/AVS indicou que pelo menos três pontos da área de estudo poderiam ser tóxicos. Em geral, a toxicidade crônica identificada nos testes biológicos não foi corroborada pela relação SEM/AVS, cuja concentração molar de metais potencialmente tóxicos (extração com HCl 6 M) foi inferior à concentração molar de monossulfetos que normalmente funcionam como ligantes destes metais nos sedimentos. Porém para a toxicidade aguda, a relação SEM/AVS mostrou concordância em 5 das 8 amostras testadas, o que sugere um poder razoável do método SEM/AVS para prever este tipo de toxicidade. Isso indica que quanto maior a disponibilidade de sítios de sulfetos para aprisionamento dos metais lábeis, menor a toxicidade aguda observada. Por outro lado, a comparação das concentrações de metais totais (e.g. Cd, Cr, Cu, Hg, Ni, Pb e Zn) com o nível de referência de contaminação (Nível 1) proposto por CONAMA 454 sugere que 7 dos 8 sedimentos são potencialmente tóxicos. Este aspecto mostrou alta concordância com a toxicidade crônica identificada. Comportamento assim revela que os efeitos crônicos possivelmente possuem relação com o fato de que os copépodos usados no estudo podem se expor e sofrer os efeitos adversos dos metais possivelmente mais solúveis na água intersticial dos sedimentos testados. Adicionalmente, a ingestão do próprio sedimento por estes organismos é outro aspecto a ser considerado. Os resultados deste estudo revelam que o método SEM/AVS prevê razoavelmente a toxicidade aguda, enquanto a excedência de Nível 1 segundo CONAMA 454 (2012) prevê muito bem toxicidade crônica dos sedimentos
Abstract: Sediments represent an important compartment to assess contamination levels of aquatic ecosystems, because it is possible to observe the accumulation and the integration of a variety of contaminants in them. The Santos-Cubatão Estuarine System (São Paulo Estate ¿ Brazil) has been pointed out as a severely polluted sedimentary environment due to the uncontrolled emission of urban and industrial effluents. Particularly in this system, the Morrão River (object of this study) has undergone the impact of activities related to fertilizers and iron industries in the last 60 years. Aiming at evaluating the quality of the sediments in this environment, a study of the toxicity and bioavailability of some contaminants and a physical-chemical characterization were carried out during the dry season, by means of sampling along mangrove margins. Several environmental parameters were assessed, including: concentrations of acid volatile monosulfides (AVS) and simultaneously extracted metals (SEM); grain size (texture characterization) and organic matter content (MO); analysis of the total chemical element concentration; and the application of acute (using Tiburonella viscana) and chronic (copepod Nitocra sp) ecotoxicity tests. The results revealed that the silt fraction is dominant in the sediments (>60% sample volume) and that MO contents range from 9.15% and 22.3%. The AVS showed concentrations between 0.43 and 41.38 µmol g?1 in the sampled points and SEM between 0.48 and 7.02 µmol g?1, suggesting that adverse effects would not be potentially expected in exposed organisms in the study area. However, tests with living organisms revealed acute toxicity in some points, whereas chronic toxicity was evident in all sampled points. The SEM/AVS method indicated that at least three points of the study area could be toxic. In general, chronic toxicity identified in the biological tests was not corroborated by the SEM/AVS ratio, once the molar concentration of potentially toxic metals (HCl 6 M extraction) was lower than the molar concentration of monosulfides that usually act as bonding agents. For the acute toxicity, the SEM/AVS ratio was concordant in 5 out of the 8 tested samples, which suggests a reasonable efficiency of the SEM/AVS method to predict this type of toxicity. The higher the availability of sulfide sites is for trapping of labile metals, the lower the acute toxicity observed. On the other hand, the comparison of the total metal concentrations (e.g. Cd, Cr, Cu, Hg, Ni, Pb and Zn) with the contamination level reference (Level 1) proposed by CONAMA 454 indicates that 7 out of the 8 sediment samples are potentially toxic. This aspect is highly concordant with the chronic toxicity identified in the study area. Such behavior reveals that the chronic effects are possibly related to the fact that the copepods used in the study can expose themselves and undergo the adverse effects of the metals that are possibly more soluble in the sediment interstitial water. Additionally, the ingestion of the sediment itself by these organisms is another aspect to be considered. The results of this study reveal that the SEM/AVS method reasonably predicts acute toxicity, whereas chronic toxicity is well assessed by contents exceeding Level 1 values
Mestrado
Geologia e Recursos Naturais
Mestra em Geociências

Orientadores: Wanilson Luiz Silva
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências
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Resumo: O sistema estuarino de Santos-Cubatão (SP) está localizado em uma das áreas mais industrializadas da América Latina. Os estuários são ambientes de grande complexidade, onde ocorrem interrelações entre componentes geológicos, físicos, biológicos e químicos. O histórico de contaminação desse ambiente estuarino, decorrente de diferentes atividades antrópicas, pode resultar em altos níveis de contaminação, e os sedimentos podem representar uma fonte latente de elementos-traço para o ambiente aquático. Com o objetivo de investigar a variabilidade geoquímica sazonal de elementos-traço, os sedimentos de superfície dos principais rios deste sistema estuarino (Casqueiro, Cubatão, Cascalho, Morrão e Capivari) foram amostrados no inverno e no verão. Concentrações químicas multi-elementares em diferentes granulometrias (<63 mm, <177 mm e total), obtidas por ICP-MS, e os níveis de matéria orgânica foram relacionados. As texturas dos sedimentos estudados apresentaram característica silto-argilosa (64 a 87%). Os maiores níveis de matéria orgânica foram encontrados nos sedimentos do rio Morrão (10,92 a 12,05%), porém não foi observada relação com a granulometria. Em geral, os metais e metalóides foram mais concentrados na textura silto-argilosa, mas isso não foi sistemático para todo o ambiente. Considerando fatores de enriquecimento, anomalias geoquímicas foram encontradas para os elementos Be, Bi, Ca, Co, Cu, Cd, Cr, Fe, Hf, Hg, Mn, Ni, Nb, P, Pb, Sb, Sr, Ta, Th, U, Y, Zn e Zr especialmente no rio Morrão. Com exceção do rio Capivari, o Hg e o P foram os únicos elementos que se apresentaram anômalos nos demais rios investigados. Elementos como Al, As, Cs, K, Li, Mg, Na, Rb, S, Ti e V apresentaram comportamento geogênico ao longo de todo o ambiente deste estudo. A sazonalidade geoquímica foi notificada claramente nos sedimentos do rio Morrão e parece não ocorrer para a maioria dos elementos tratados nos demais rios investigados. Em geral, foi observado um maior enriquecimento dos elementos contaminantes durante o verão, provocando uma diminuição relativa dos elementos geogênicos nesta estação. O contrário ocorreu durante o inverno. Este trabalho mostrou que o incremento nos níveis de contaminação favorece a flutuação sazonal das concentrações de elementos nos sedimentos. Possivelmente, a sazonalidade associada aos elementos contaminantes pode estar ligada ao fato de estes elementos ocuparem posições mais instáveis em fases minerais e não-minerais do ambiente sedimentar. Isso possibilita uma maior mobilização da carga de elementos contaminantes em função das variações das condições físicas e/ou químicas do meio (pH, Eh, salinidade), se comparada aos elementos geogênicos mais estáveis no ambiente.
Abstract: The Santos-Cubatão estuarine system (SP) is located in one of the most industrial areas in Latin America. Estuaries are environments of great complexity where there is an interrelation among geological, physical, biological, and chemical compounds. The contamination history at this environment is a result of different anthropic activities which can be high, and the sediments can represent a significant source of trace elements to aquatic environment. By investigating the seasonal geochemical range of trace elements, the surface sediments of the main rivers from this estuarine system (Casqueiro, Cubatão, Cascalho, Morrão, and Capivari) were sampled in the winter and summer. Multi-elemental chemical concentrations in different grain-size (<63 mm, <177 mm and total), gotten by ICP-MS, and the organic matter level were related. The texture of the studied sediments presented silt-clay characteristics (64 to 87%). The highest levels of organic matter were found in the sediments of Morrão River (10.92 to 12.05%), however, no direct relation with the grain-size. In general, the metals and metalloids were more concentrated in the siltclay texture, but it was not systematic to the entire estuary. Regarding enrichment factors, geochemical anomalies were found to the following elements Be, Bi, Ca, Co, Cu, Cd, Cr, Fe, Hf, Hg, Mn, Ni, Nb, P, Pb, Sb, Sr, Ta, Th, U, Y, Zn, and Zr, mainly in Morrão River. The only elements that were presented anomalous in every river studied, except in Capivari River, were Hg and P. Elements as Al, As, Cs, K, Li, Mg, Na, Rb, S, Ti, and V presented geogenic behavior all along the environment of this study. The geochemical seasonality was clearly seen in the sediments of Morrão River, but not conclusive to most elements in the other rivers. In general, it was observed a higher enrichment of contaminant elements during the summer, causing a relatively decrease of geogenic elements in that season. However, the opposite happened during the winter. This work shows that the increment in the contamination level contributes to the seasonal fluctuation of the element concentrations in the sediments (e.g. Morrão River). The seasonality associated to the contaminant elements can be regarded to the fact that these elements occupy more unstable positions in mineral and non-mineral phases of the sedimentary environment, leading to a great mobilization of contaminant elements load caused by the physical and/or chemical range of conditions of the environment (mainly, pH, Eh and salinity), when compared to the more stable geogenic elements in the environment.
Mestrado
Geologia e Recursos Naturais
Mestre em Geociências

Microbial biogeography explores the spatial and temporal distribution of microorganisms at multiple scales and is influenced by environmental selection and passive dispersal. Understanding the relative contribution of these factors can be challenging as their effects can be difficult to differentiate. Dormant thermophilic endospores in cold sediments offer a natural model for studies focusing on passive dispersal. Understanding distributions of these endospores is not confounded by the influence of environmental selection; rather their occurrence is due exclusively to passive transport. Sediment heating experiments were designed to investigate the dispersal histories of various thermophilic spore-forming Firmicutes in the River Tyne, a tidal estuary in North East England linking inland tributaries with the North Sea. Microcosm incubations at 50-80°C were monitored for sulfate reduction and enriched bacterial populations were characterised using denaturing gradient gel electrophoresis, functional gene clone libraries and high-throughput sequencing. The distribution of thermophilic endospores among different locations along the estuary was spatially variable, indicating that dispersal vectors originating in both warm terrestrial and marine habitats contribute to microbial diversity in estuarine and marine environments. In addition to their persistence in cold sediments, some endospores displayed a remarkable heat-resistance surviving multiple rounds of autoclaving. These extremely heat-resistant endospores are genetically similar to those detected in deep subsurface environments, including geothermal groundwater investigated from a nearby terrestrial borehole drilled to >1800 m depth with bottom temperatures in excess of 70°C. The ability of these endospores to survive extreme temperatures whilst in a dormant state may enable them to withstand adverse conditions for long periods of time and then germinate in response to changing surroundings. This was investigated further in the context of seawater injection during secondary oil recovery, where cold seawater is injected into hot oil reservoirs, resulting in a cooler reservoir temperature near the injection well bore. Microcosm experiments designed to simulate this showed that cooling triggered the germination of endospores of sulfate-reducing Desulfotomaculum leading to the onset of souring in this model system. The results presented here, indicate that bacterial endospores are transported between terrestrial and marine, surface and subsurface environments. Their survival and distribution therefore has ii relevance to understanding deep biosphere processes, and factors shaping microbial diversity in the marine environment.

To date, research on the fate of methane in marine settings has mainly focused on anaerobic microbial processes. An alternative fate for methane is aerobic methane oxidation (AMO) by methanotrophic bacteria which takes place in aerobic surface sediments and the overlying water column. Tracing methanotroph activity in past environments can be achieved via analysis of a distinctive suite of biomarkers called bacteriohopanepolyols (BHPs). BHPs are membrane lipids produced by many prokaryotes comprising a pentacyclic triterpenoid structure with an extended polyfunctionalised side chain. Although, there is much debate about the role of BHPs, studies suggest they regulate cell membrane fluidity, however, the factors controlling their expression are poorly constrained. They have a wide range of structural variation which varies between bacterial phyla and species. The major BHPs produced by methanotrophs are collectively known as the 35-aminoBHPs, most commonly including 35-aminobacteriohopane-32,33,34-triol (aminotriol), 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol) and 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), with aminopentol seen as a diagnostic marker for Type I methanotrophs from the phylum Gammaproteobacteria. The changes in methanotroph community composition in estuarine sediments under a range of environmental perturbations and the effect this had on BHP composition, namely the 35-aminoBHPs, was assessed. Aerobic microcosms inoculated with River Tyne (UK) estuarine sediment with a 5% methane amended headspace (unless otherwise stated), were subjected to a range of environmental perturbations; methane concentration (0.1-5%), temperature (4-60°C), pH (4-9) and salinity (1-150 g/L NaCl). Methane oxidation rates were monitored and methanotroph diversity was determined by targeting the particulate methane monooxygenase gene (pmoA). Methane oxidation was observed between 4 and 50°C, at all tested pH values and up to salinities of 70 g/L; however, methanotroph community composition varied with temperature, pH and salinity and these changes were reflected in the 35-aminoBHP signatures quantified by LC-MS analysis. For example, aminopentol was not enriched at pH 9 when the unusual Type I Methylomicrobium spp. were dominant, whilst the maximal production of C-3 methylated aminopentol was witnessed at 50°C when a Methylocaldum sp. was enriched. The hpnR gene, required for the methylation of BHPs at the C-3 position, was also identified in sediments at the aforementioned temperature. Novel iv compounds, identified after the analysis of six previously untested Type I marine methanotrophs within this study, were also found in microcosm sediments in varying abundances. The effect that of growth stage on 35-aminoBHP abundance was determined by analysing aerobic microcosms inoculated with River Tyne estuarine sediment over a 28 day period at times before and after methane oxidation. It revealed the continued production of aminopentol at mesophilic temperatures after methane oxidation was complete. This may have implications for the interpretation of the sedimentary record where aminopentol witnessed in marine settings may not represent periods of significant methane oxidation but rather a response to methane limiting conditions. Anaerobic producers of BHPs were investigated and the preservation and/or degradation of individual compounds was assessed in long-term studies. Microcosms inoculated with anoxic River Tyne estuarine sediment were subjected to sulphate-reducing and methanogenic conditions over a period of 706 and 665 days respectively. Changes in BHP composition over time were quantified by LC-MS with compounds including bacteriohopane-32,33,34,35-tetrol (BHT) and adenosylhopane found to be more resistant to degradation over the course of the study compared to bacteriohopane-32,33,34,35-tetrol cyclitol ether (BHT cyclitol ether). This indicates that some compounds are more resistant to degradation over time compared with others.

Intertidal sediments of modern British and Irish estuaries and embayments have been analysed to investigate the degree to which such deposits are characterised by their palynomorph assemblages. Localities selected for study were: the Ythan Estuary, Aberdeenshire; the Montrose Basin, Angus; Chichester Water, Sussex; the Tresillian and Fal estuaries, Cornwall; the Shannon and Clarinbridge estuaries, Ireland; and numerous estuaries feeding into the Solway Firth. At the head of a typical estuary there is a sharp and conspicuous change in the palynomorph assemblages: brackish and marine palynomorphs are abundant throughout the tidally influenced reaches whereas, except for a few specimens probably brought in by birds or other animals, they are absent upstream of the tidal limit. In general, marine and brackish forms show few distinguishable trends in distribution between the head and mouth of the estuary, being evenly spread by tidal flushing. Dinoflagellate cysts, for example, are as abundant in the upper reaches as they are downstream. The marine/estuarine transition is poorly characterised by changes in palynomorph assemblages. Relative proportions of most of the terrestrially-derived palynomorphs increase upstream although woody fragments have a greater relative abundance in the lower reaches, possibly because they are more resistant and can remain in suspension longer than most other types of plant debris. Biogenic pyrite and invertebrate faecal material both occur more commonly in estuarine deposits than in fluvial deposits. The samples contain a mixture of marine and brackish organisms and terrestrial palynomorphs. An eider duck faecal pellet, collected from the Ythan Estuary, contained a diverse palynomorph assemblage similar to that of the intertidal mud samples. Freshwater species are rare in intertidal deposits and comprise mainly turbellarian egg cases. Almost all aquatic palynomorphs present in the samples have been recorded by other workers from marine sediments. Of those which appear to be restricted to environments of reduced salinity, most are eggs or egg cases and one of these is described for the first time (Palynomorph Y). Fluvial and lacustrine samples contain terrestrial palynomorphs, turbellarian cocoons and a small number of unidentified cyst-like structures. An incidental observation showed that, on gentle heating, dinoflagellate cysts that had undergone palynological processing dehisced and released their cell contents. This may be a physical response of the cyst to heat, by expanding and rupturing, or the cysts may be sensing a 'spring' temperature rise and attempting to hatch. The viability of the emergent protoplasm is unknown. The contents of the thesis will help to refine the use of palynomorph assemblages in the reconstruction and predictive modelling of Quarternary and perhaps older depositional environments, in particular, in distinguishing estuarine sediments from fully marine and freshwater sediments.

Sediments and pore waters from two urban estuaries ranging in sediment mixing energy were studied to evaluate the potential release of contaminants from particles during sediment diagenesis. Two sites in Elizabeth River, VA and two tributaries in the Hudson River Watershed were sampled for polycyclic aromatic hydrocarbons (PAHs). Sediment age, total sediment organic carbon (TOC), carbon to nitrogen (C/N) ratios, and particle surface area (SA) were also sampled at these sites. In the Elizabeth River, both sites sampled (Site 1 and Site 2) have been non-depositional for the past 70 y or are comprised of old dredge spoil. PAH K&\sp\prime\sb{lcub}\rm OC{rcub}&s were significantly higher at Site 2 than Site 1 indicating a different type of particle-PAH association at each site independent of the amount of TOC. Decreasing down-core K&\sp\prime\sb{lcub}\rm OC{rcub}&s at Site 1 coincided with down-core change in TOC accessible for PAH binding. at Site 2 in the Elizabeth River, high and uniform K&\sp\prime\sb{lcub}\rm OC{rcub}&s may have resulted from particles with PAHs entrapped by an organic coating. Deposition rates in the East River and Newark Bay were calculated to be &\sim&27 cm/y and &\sim&2 cm/y, respectively. Sediment PAH concentrations were significantly higher in the East River than Newark Bay, coincident with the higher amounts of TOC and SA in East River sediments. Low molecular weight PAHs were not detectable in East River sediments and PAHs were not detectable in East River pore waters. The East River seems to be a site of intense physical mixing where pore water PAHs possibly bound to DOC may be continuously mobilized out of the seabed. In contrast, PAHs in Newark Bay sediments are able to attain equilibrium due to lower intensity of physical mixing. Aspects of sediment geochemistry such as the occlusion of TOC for PAH binding, particle porosity, and amount of pore water DOC may affect PAH distributions in areas where the physical energy of mixing is infrequent or low. PAH distributions in areas that are subject to high energy physical disturbances, may be controlled by the physical energy affecting the system rather than compositional aspects of particulate or pore water dissolved organic matter.

The increasing interest in the use of palacoenvironmental indicators and in particular diatoms to reconstruct past changes in sea level has highlighted the need for a more precise methodology that (a) provides quantitative reconstructions, and (b) is applicable to a wide range of sedimentary environments. Despite the widespread and increasing recent interest in the use of diatoms as indicators of estuarinep alaeoenvironmentsa nd sea-levelc hange,e xisting interpretative models, basedo n simple classification of taxa into freshwater, brackish or marine forms, provide only _qualitative estimates of past conditions. Resulting palaeoenvironmental reconstructions are at best crude, offering some indication of past mean sea level height, and at worst erroneous, as they fail to consider the effect of post-mortem transport and other taphonomic processes. This study aims to address these problems for the coast of Britain by developing a more robust quantitative method for using diatoms as indicators of estuarine palaeoenvironments and sea-level change. More specifically, it aims to develop a quantitative predictive model (transfer function) that relatesd iatom assemblagec omposition to salinity, habitat, depositional environment and tidal level around the coast of Britain. This is done through the collection and analysis of a training data set of diatom assemblagesa nd environmental variables (salinity class, elevation, grain size, habitat type and sediment organic content) from 25 sites around the coast of Britain. Qualitative and quantitative relationships within the diatom assemblagesa nd between the diatom assemblagesa nd coastale nvironmentalv ariables are explored using TWINSPAN and canonical correspondencea nalysisr espectively. The key environmental variables driving diatom assemblagesin the intertidal environment are shown to be elevation, salinity and sediment particle size. Habitat type and site location also explain a significant amount of variation in the diatom data, suggestingr egional differences in diatom assemblagesn ot accounted for by geornorphological and sedimentological differences between sites. The final transfer function for inferring normalised tidal height has a root mean squared error (RMSE) of 0.26, and a squared correlation (1-2) between observed and diatom-inferred normalised tidal height of 0.61. Corresponding error estimates under cross-validation by leave-one-out are 0.34 and 0.35 for RMSEjack and rjack 2 respectively. The poor performance of the model in comparison to published regional transfer functions is concluded to be due to the mergt:i In g of data from a large number of sites over a large geographical area. Such merging - has apparently introduced a large amount of noise into the diatom / elevation relationship, and is probably related to the increased heterogeneity and interaction of sediment typeý and elevation, and to the observed regional overprint in the diatom assemblages. Analogue matching to infer Sample habitats from the diatom data performs with a success Z): rate of 59%. Further merging of the habitat types based on ecologically similarities increases the success rate to 82%. The correct scale of trade off between coverage of palaeoenvironments, fossil diatom species 4): and reduction of regionality in the modem training dataset is an issue that needs further research before this model may be applied to core material to assist in palaeoenvironmental reconstructions.

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.

Microbiological water quality monitoring of bathing waters does not account for faecal bacteria in sediments. Intertidal deposits are a significant reservoir of faecal bacteria and this indicates there is a risk to human health through direct contact with the sediment, or through the resuspension of bacteria to the water column. This project investigated factors influencing the relative abundance of faecal indicator organisms (FIOs) in intertidal estuarine sediments. The effects of physical, biogeochemical and biological sediment characteristics, environmental variables and native microbial communities were explored through field campaigns on the Ythan and Eden estuaries, Scotland. The contributory role of sediments to adverse water quality was investigated by combining FIO abundance and measurements of sediment stability. The importance of strain and sediment characteristics in the adhesion of E. coli to suspended sediments was also examined using laboratory experiments. E. coli concentrations up to 5.9 log₁₀ CFU 100 g dry wt⁻¹ were observed, confirming that intertidal sediments are an important reservoir of faecal bacteria. The variability of E. coli abundance in estuarine sediments was successfully explained with multiple stepwise linear regression (Adjusted R² up to 87.4) using easily-obtainable measurements of sediment characteristics and environmental variables, with variability most heavily influenced by salinity and particle size gradients. Native microbial community population metrics and community constituent composition correlated with environmental gradients, but did not influence FIO abundance. The amount of E. coli adhering to suspended sediments ranged from 0.02 to 0.74 log₁₀ CFU ml⁻¹, and was dependant on strain characteristics and sediment type rather than zeta potential, with higher cell-particle adhesion at 2 and 3.5 PSU than 0 and 5 PSU. Monitoring of sediment characteristics will lead to more informed bathing water quality advisories to protect public health. Future research should focus on applying the findings here to the modelling of bacterial fate and transport on a catchment scale.

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 (