Nearly thirty C20, C25, and C30 highly branched isoprenoid (HBI) hydrocarbons have been detected, sometimes in high concentrations, in recent freshwater, estuarine, coastal and hypersaline sediments, and water column particulate matter from numerous locations worldwide. The parent structures have been proved but only a few of the double bond positions have been established. The assignment of C21, C22 and C26 homologues and other C20 and C25 isomers, remains tentative. A wide body of evidence suggests that the compounds are biogenic in origin, with algae and possibly bacteria the most likely source organisms. A few of the compounds have been identified in field samples of algae but none have been reported in laboratory cultured biota. The alkenes with more than two double bonds appear to be rapidly removed from the hydrocarbon fraction in most sediments, whereas the alkanes and monoenes seem to be more resistant to biodegradation and hence occur in some more ancient sediments and oils. There is evidence that some of the alkenes react rapidly with sulphur to form either S-containing HBI heterocycles or become bound within macromolecular aggregates both found in sediments and some oils. The compounds, both as hydrocarbons and S-containing analogues, may prove useful environmental indicators once the sources and exact structures of more of them have been established. In the literature the structural elucidation of C25 and C30 alkenes has been based mainly on the analysis of their hydrogenation products. However, some authors concluded that the alkenes are cyclic since some could not be fully hydrogenated. The structure of a C25 HBI diene was proven to be a cyclic by hydrogenation studies and GC and GCMS analyses which showed the HBI compound to be fully saturated. The isolation and characterisation of synthetic alkenes resulted in the assignment, or partial assignment, of structures to four C20, six C25 and four C30 monoenes. The formation of novel monoenes via isomerisation reactions has also been achieved. The compounds form a valuable database of chromatographic and spectroscopic information for the assignment of sedimentary alkenes but the importance of isolation and micro-ozonolysis has been emphasised. Synthetic HBI alkenes were used to assign structures and partial structures to naturally occurring HBI hydrocarbons in three sediments. Other monoenes (both with methylene double bonds) were isolated from the sediments and characterised using spectroscopic and micro-ozonolysis data. The widespread occurrence of C20 and C23 HBI hydrocarbons in Tamar sediments and associated algae (macrophytes and diatoms), the large variation in isotopic composition evident for the C20 monoene, and the seasonal sedimentary distribution all suggest two possible sources for the HBI hydrocarbons; microalgae and/or heterotrophic bacteria. Investigation of the distribution of hydrocarbons from the Peru upwelling area confirmed the rapid decrease in concentration of C25 HBI alkenes with depth. A mixture of HBI monoenes was successfully incorporated into melanoidins but not detected in the humic acid pyrolysate which implied that incorporation of HBI alkenes into accreting humic substances was not a major mechanism of diagenesis of HBI alkenes. This study has extended present knowledge of the structures of HBI monoenes and has suggested two possible biological sources. There is still much to be learned about HBI polyenes and the subject is proving to be a fruitful area for further research into biomarker potential. Some possible future approaches are suggested.

Thesis (Ph. D.)--University of Rhode Island, 2006. / Typescript. Includes bibliographical references (leaves 140-150).

The rise in global energy demand has motivated the exploration and production of oil and gas in increasingly challenging marine environments and there is a continuous risk of accidental oil spills. One of the many fates of spilled oil is deposition on the seabed, which has been extensively studied following the Deepwater Horizon oil spill. However, post-depositional fates of oil in sediments are not well understood. Similarly, the effects of chemical dispersant on oil fate are currently under investigation as their overall contribution to mitigating oil spills environmental impacts remains debated. This project aimed to evaluate the potential for spilled oil to entrain marine sediments and the effects dispersant application had on the process under three transport regimes; (1) post-depositional transport via oil-sediment aggregate deposition in deep-sea sediments, (2) percolative transport in intertidal sands and (3) advective pore-water transport in intertidal and subtidal sands. Investigations into the sorption dynamics of two polyaromatic hydrocarbons in sediment-dispersantseawater systems were also undertaken to evaluate the influence of dispersant application on sorption of hydrocarbons to sediments. Finally, the effects of oil exposure at in situ conditions of pressure and temperature on sediment bacterial community composition were investigated. Oil transport experiments revealed that the tested regimes resulted in significant entrainment of hydrocarbons in marine sediments. Dispersant application resulted in enhanced oil entrainment into sands but not in silts and this effect depended on the water-solubility of hydrocarbons. Watersoluble components were less affected by dispersant than less water-soluble ones. Investigations into sediment bacterial responses to oil exposure at in situ conditions of pressure and temperature revealed a significant effect of both variables on diversity and community composition, highlighting the importance of conducting deep-sea microbial studies at conditions as close to in situ as possible.

Thesis (M.Sc.)--University of Guelph (Ont.), 2001. / Adviser: Ray Kostaschuk. Includes bibliographical references.

Thesis (M.Sc.)--Memorial University of Newfoundland, 1997. / Bibliography: leaves 87-98.

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.

Derramamentos de petróleo geraram o aumento da atenção de órgãos governamentais e civis quanto a estudos e técnicas para minimizar os danos aos recursos ambientais e socioeconômicos causados por este tipo de acidente. O desenvolvimento de técnicas e os estudos relacionados à prevenção e resposta aos acidentes busca maior eficiência na resposta à contingência e à diminuição dos danos ambientais e socioeconômicos causados na área atingida. A Carta de Sensibilidade Ambiental ao Derramamento de Óleo (Carta SAO) é uma importante ferramenta para a diminuição de danos causados ao ambiente, para o planejamento ambiental na prevenção e na reposta a acidentes em locais de armazenamento e transporte de hidrocarbonetos, tais como dutos, ferrovias, rodovias, etc. Na Carta SAO, para áreas de exposição de sedimentos e rochas sedimentares, procura-se quantificar e qualificar uma determinada área que apresente vulnerabilidade e sensibilidade ao óleo, ou seja, estipular a área e as características intrínsecas do terreno que apresenta alguma probabilidade de ser atingido por óleo, considerando também atividades de resposta. As características dos sedimentos existentes em áreas vulneráveis permitem a determinação de sua sensibilidade, assim buscou-se estudar os parâmetros sedimentares mais influentes na determinação da sensibilidade ambiental do terreno, como a granulometria e seleção, os quais influenciam a porosidade e permeabilidade do terreno, e o cruzamento dessas informações com a declividade do terreno. A fim de testar a eficiência desses parâmetros, o estudo foi aplicado na Bacia do Ribeirão Tamanduá, na região de Cravinhos (SP), por ser interceptada pelo Duto OSBRA e a área de exposição dos arenitos da Formação Botucatu. / Oil spills have resulted in increased awareness among government and private agencies regarding studies and techniques to minimize damages caused by this type of accident to environmental and socio-economic resources. The development of techniques and the studies for prevention and response to accidents is intended to achieve greater effectiveness in dealing with this type of contingency and to decrease the environmental and socio-economic damage to the areas affected by oil spills. The Environmental Sensitivity Index Map for Oil Spills (ESI Map) is an important tool that helps to decrease the damage caused to the environment. It is also useful in planning prevention and responding to accidents in storage areas and in transporting hydrocarbons, in ducts, by rail, road, etc. The purpose of the ESI Map is to quantify and qualify certain areas of exposed sediments and sedimentary rocks that are vulnerable or present sensitivity to oil. In other words, stipulate the area and the intrinsic characteristics of the ground that may receive an oil spill, and considering the response actions. The characteristics of existing sediments in vulnerable areas allow the determination of the area\'s sensitivity. As a result, the study focused on the sedimentary parameters with greatest influence in determining the area\'s environmental sensitivity, such as granulometry and grain selection, which have an influence in the ground\'s porosity and permeability, and cross-referencing this information with the declivity of the ground. In order to test the efficiency of these parameters, the study was implemented in the Bacia do Ribeirão do Tamanduá, in the Cravinhos (SP) region, because it intercepts the OSBRA oil pipeline and an area with exposed sandstone from the Botucatu Formation.

Thesis (M.S.) -- University of Tennessee, Knoxville, 2006. / Title from title page screen (viewed on Sept. 19, 2006). Thesis advisor: Joanne Logan. Vita. Includes bibliographical references.

Derramamentos de petróleo geraram o aumento da atenção de órgãos governamentais e civis quanto a estudos e técnicas para minimizar os danos aos recursos ambientais e socioeconômicos causados por este tipo de acidente. O desenvolvimento de técnicas e os estudos relacionados à prevenção e resposta aos acidentes busca maior eficiência na resposta à contingência e à diminuição dos danos ambientais e socioeconômicos causados na área atingida. A Carta de Sensibilidade Ambiental ao Derramamento de Óleo (Carta SAO) é uma importante ferramenta para a diminuição de danos causados ao ambiente, para o planejamento ambiental na prevenção e na reposta a acidentes em locais de armazenamento e transporte de hidrocarbonetos, tais como dutos, ferrovias, rodovias, etc. Na Carta SAO, para áreas de exposição de sedimentos e rochas sedimentares, procura-se quantificar e qualificar uma determinada área que apresente vulnerabilidade e sensibilidade ao óleo, ou seja, estipular a área e as características intrínsecas do terreno que apresenta alguma probabilidade de ser atingido por óleo, considerando também atividades de resposta. As características dos sedimentos existentes em áreas vulneráveis permitem a determinação de sua sensibilidade, assim buscou-se estudar os parâmetros sedimentares mais influentes na determinação da sensibilidade ambiental do terreno, como a granulometria e seleção, os quais influenciam a porosidade e permeabilidade do terreno, e o cruzamento dessas informações com a declividade do terreno. A fim de testar a eficiência desses parâmetros, o estudo foi aplicado na Bacia do Ribeirão Tamanduá, na região de Cravinhos (SP), por ser interceptada pelo Duto OSBRA e a área de exposição dos arenitos da Formação Botucatu. / Oil spills have resulted in increased awareness among government and private agencies regarding studies and techniques to minimize damages caused by this type of accident to environmental and socio-economic resources. The development of techniques and the studies for prevention and response to accidents is intended to achieve greater effectiveness in dealing with this type of contingency and to decrease the environmental and socio-economic damage to the areas affected by oil spills. The Environmental Sensitivity Index Map for Oil Spills (ESI Map) is an important tool that helps to decrease the damage caused to the environment. It is also useful in planning prevention and responding to accidents in storage areas and in transporting hydrocarbons, in ducts, by rail, road, etc. The purpose of the ESI Map is to quantify and qualify certain areas of exposed sediments and sedimentary rocks that are vulnerable or present sensitivity to oil. In other words, stipulate the area and the intrinsic characteristics of the ground that may receive an oil spill, and considering the response actions. The characteristics of existing sediments in vulnerable areas allow the determination of the area\'s sensitivity. As a result, the study focused on the sedimentary parameters with greatest influence in determining the area\'s environmental sensitivity, such as granulometry and grain selection, which have an influence in the ground\'s porosity and permeability, and cross-referencing this information with the declivity of the ground. In order to test the efficiency of these parameters, the study was implemented in the Bacia do Ribeirão do Tamanduá, in the Cravinhos (SP) region, because it intercepts the OSBRA oil pipeline and an area with exposed sandstone from the Botucatu Formation.