Thesis (Ph. D.)--Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2012. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Driven by increasingly heavy oil reserves and more efficient refining technologies, use of heavy fuel oils for power generation is rising. Unlike other refined products and crude oils, a large portion of these heavy oils is undetectable using the traditional gas chromatography-based techniques on which oil spill science has been based. In the current study, samples collected after the 2007 M/V Cosco Busan heavy fuel oil spill (San Francisco, CA) were analyzed using gas chromatography (GC)-based techniques, numerical modeling and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to examine natural weathering of the oil over a one and a half year period. Traditional GC techniques detected variable evidence of evaporation/ dissolution, biodegradation and photodegradation. Petroleum hydrocarbon compounds smaller than -n-C 16 were rapidly lost due to evaporation and dissolution. Significant biodegradation was not detected until one month post spill while photodegradation was only observed at one field site. To further examine the processes of evaporation and dissolution, samples were analyzed with comprehensive two-dimensional GC (GCxGC) and a physiochemical model developed to approximate quantitative apportionment of compounds lost to the atmosphere and water. Model results suggest temperature is the primary control of evaporation. Finally, to examine the prominent non-GC amenable component of the oil, samples were analyzed with FT-ICR MS. Results showed expected clustering of samples, with those samples collected sooner after the spill having the most compositional similarity to the unweathered oil. Analysis of dominant heteroatom classes within the oil showed losses of high molecular weight species and the formation of stable core structures with time. These results highlight the susceptibility to weathering of these higher molecular weight components, previously believed to be recalcitrant in the environment. Research findings indicate that environmental weathering results in removal or alteration of larger alkylated compounds as well as loss of lower molecular weight species through evaporation/dissolution, biodegradation and photodegradation, with a resultant fraction of stable compounds likely to remain in the environment years after the spill. This research demonstrates the advantages of combining multiple analytical and modeling approaches for a fuller understanding of oil spill chemistry. / by Karin Lydia Lemkau. / Ph.D.

O Canal de São Sebastião, localizado na costa norte de São Paulo, na região dos municípios de Ilhabela e São Sebastião, é uma das mais importantes zonas costeiras do Estado de São Paulo, em termos de biodiversidade. O Terminal Marítimo Almirante Barroso ? Dutos e Terminais do Centro-Sul (TEBAR/ DTCS) da PETROBRAS está localizado nesta região, na qual ocorreram 151 vazamentos de óleo ligados ao transporte marítimo entre 1978 e 2002. O monitoramento dos costões rochosos do Canal de São Sebastião foi criado pela CETESB para levantar dados de base sobre as comunidades de costões entremarés visando subsidiar futuras avaliações dos impactos de vazamentos de óleo na região. Foram monitorados 17 costões durante quatro anos, entre 1993 e 1996. Constatou-se a presença de 287 táxons (macrofauna e macroalgas), com marcante variação na composição de espécies entre os costões. A estrutura taxonômica de grandes grupos e trófica, no entanto, mantiveram-se relativamente homogêneas entre os pontos. Apesar de haver algumas diferenças locais, o padrão geral de zonação foi similar entre os costões, variando principalmente a largura dos estratos e a composição das espécies acompanhantes. As variações quantitativas das espécies dominantes foram intensas entre os pontos e reduzidas sazonalmente. Os parâmetros ambientais identificados como mais significativos no controle da estrutura da comunidade foram hidrodinamismo, declive, e quantidade de refúgios na rocha. Foram constatadas preferências diferenciadas pelas espécies dominantes por combinações ambientais específicas. / The São Sebastião Channel, located at the north coast of São Paulo State, between the cities of Ilhabela and São Sebastião, is one of the most important coastal zones of the State regarding biodiversity. The Almirante Barroso maritime terminal TEBAR/DTCS is located at this area, where 151 oil spills occurred over the last 25 years. The São Sebastião Channel rocky shore monitoring program was created in order to generate background data about the intertidal community and to support future evaluations of ecological impacts from oil spills. Seventeen sites were monitored during four years (1993-1996). This program registered 287 taxa (macrofauna and macroalgae), and great variation on the species composition among the sites. However, the taxonomic and trophic structure was very similar. Despite the occurrence of individual differences, such as belts width and the composition of the less dominant species, the general pattern of vertical zonation was similar among sites. The quantitative variations of the dominant taxa were intense among the different rocky shores but small seasonally. The environmental variables identified as the most important to the community structure were the hydrodynamics, slope and rock heterogeneities (refuges). The existence of an ecological gradient reflecting the environmental preferences of the dominant species was clearly indicated in this study.

Graduation date: 1995

Univ., Diss.--Hamburg, 2006. / Literaturverz. S. [215] - 225.

Made available in DSpace on 2014-06-11T19:26:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-03-09Bitstream added on 2014-06-13T20:54:20Z : No. of bitstreams: 1 cunha_fp_me_rcla.pdf: 2839508 bytes, checksum: 97928093c5d18d9ee0ea47cf2c1a067b (MD5) / O presente trabalho realizou o mapeamento de Sensibilidade Ambiental a derramamentos de óleo da região costeira do município de Bertioga-SP. Foram mapeados os ambientes do estuário do Canal de Bertioga e do Rio Itapanhau, além da área costeira marinha compreendida entre a foz do Canal de Bertioga e a Ponta do Itaguá, na praia da Boracéia, em São Sebastião. Para tanto, foi aplicada a metodologia indicada pelo Ministério do Meio Ambiente, atualmente utilizada no Brasil. Foram mapeados e identificados em campo e na literatura três tipos de informações principais: recursos biológicos; caracterização física do meio e usos humanos dos espaços e recursos (atividades sócio-econômicas). Como produto final, os ecossistemas costeiros e marinhos presentes na linha de costa foram classificados de acordo com o índice de sensibilidade ambiental. Foi desenvolvido um banco de dados geográfico e elaborado um Atlas da região contendo as cartas de sensibilidade ambiental (Cartas SAO), sendo 03 de nível tático (1:70.000) e 11 de nível operacional (1:20.000), informações descritivas dos segmentos da linha de costa, com recursos visuais, além de uma listagem de espécies. A região costeira de Bertioga apresentou significativa heterogeneidade ambiental, em sua maior parte representados por manguezal, com alta sensibilidade ao óleo, localizada em áreas do estuário. Estes ambientes apresentam baixo hidrodinamismo, sedimentos lamosos inconsolidados, de baixa declividade, abrigando grande diversidade de fauna, resultando em grande persistência do óleo no ambiente e dificultando as ações de combate. O ambiente praial demonstrou baixa variação morfodinâmica (ângulo de declividade e granulometria) sazonal, e conseqüentemente, não houve variação sazonal na classificação no índice de sensibilidade ambiental (ISL). Foi possível identificar uma lacuna na literatura científica... / This present study performed the environmental sensitivity mapping for oil spills of the coast side of Bertioga City. It has been mapped the estuary of Bertioga´s Channel and Itapanhau River, besides the marine coast side between the Bertioga´s Channel mouth and Ponta do Itaguá, at Boracéia beach, at São Sebastião City. To perform the present study it was applied the methodology indicated by the Ministry of the Environment, currently used in Brazil. It has been mapped and identified in field and literature three types of main information: biological resources, physical environment characterization and human land use and resources (socio-economic activities). As a final product it was developed a geographic database and an atlas of the surroundings containing ESI maps, including 03 tactical (1:70.000) and 11 operational maps (1:10.000), which show coast line descriptive information, visual resources and a list of biological species. The seashore of Bertioga City presents significant environmental diversity, the most part represented by mangrove ecosystem, with high sensitivity to oil, located at estuary. These environments present low hydrodynamism, mud sediment, low declivity, sheltering biodiversity, resulting in high oil persistence in environment difficulting actions to combat. The beach environment showed low seasonal morfodynamic variation, consequently, there was no seasonal variation at environmental sensitivity index. It was possible to identify a blank at scientific literature about biodiversity information for the studied area, despite being an exuberant environment. The study area has potential sources of pollution, as OSBAT pipeline and state highways. The building of a geographic database, directed to detailded ESI maps associated with an environmental atlas, showed to be an instrument for to guide actions in oil spills sceneries, while they are instruments... (Complete abstract click electronic access below)

[pt] Com a probabilidade de ocorrer derrames de óleo em águas marinhas e a carência de informação sobre o comportamento de metais neste evento, viu-se a necessidade de se intensificar estudos referentes aos complexos metálicos, para que se possa entender a competição entre os ligantes do petróleo e os ligantes da água do mar. Para isto é necessário determinar a estabilidade dos complexos formados no petróleo, compará-los com os correspondentes na água do mar. Neste trabalho foram estudados os sistemas binários de complexos de ácido hexanóico (ligante que representa os ácidos carboxílicos do petróleo) e 1-propanotiol (representante das mercaptans) com os íons metálicos de interesse para a indústria do petróleo - Ni(II), V(IV) e Fe(II) - por estarem presentes em maior quantidade. Embora presentes em menor quantidade, Cd(II) e Pb(II) foram estudados por serem metais tóxicos e controlados pelas organizações ambientais. O ácido hexanóico apresenta o oxigênio do grupamento carboxilato, como sítio de coordenação enquanto que o 1-propanotiol possui o enxofre do grupamento tiol. O estudo da complexação foi realizado em solução utilizando a titulação potenciométrica e a espectrofotometria de ultravioleta- visível, Foram calculadas as constantes de dissociação dos ligantes e de formação dos complexos ML, ML2, ML3, MLOH, ML(OH)2, ML(OH)3, ML2OH, ML2(OH)2, ML3OH. Os valores das constantes de estabilidade dos complexos poderiam ser divididos em dois grupos: o dos complexos binários com ácido hexanóico e os complexos binários do 1- propanotiol. Dos complexos formados com o ácido hexanóico, a espécie ML com o íon metálico Pb(II) foi que apresentou maior estabilidade. No sistema onde temse complexos com 1-propanotiol, a espécie ML do íon metálico Cd(II) foi o que apresentou maior estabilidade. Na distribuição de espécies com ligantes representantes do petróleo e ligantes da água do mar observou-se a formação de complexos em pH = 7 para os íon metálicos V(IV), Ni(II) e Fe(II) com o ácido hexanóico. Para o íon metálico Pb(II) o complexo formado foi com o 1- propanotiol. Já para o íon Cd(II) houve a formação de complexo com o cloreto. Para o íon Cd(II), neste pH houve formação de pouca proporção de complexos com 1-propanotiol e um percentual maior (60 por cento) de complexos com os íons cloreto e sulfato da água do mar. Entretanto, como a concentração de cádmio é em torno de ppb no óleo combustível, este valor tem pouca relevância em termos de poluição. Assim, se estes ligantes estudados, que são monodentados, ligam-se preferencialmente aos metais do que os ligantes da água, com certeza isto acontece com os ligantes polidentados do petróleo como por exemplo as porfirinas. Com a utilização da técnica de espectrofotometria de ultravioletavisível foi possível observar as bandas referentes a transferência de carga e banda d-d. Foi realizada também uma simulação de derrame de óleo combustível. Para isto analisou-se a concentração de metais foi medida em tempos variados. Os dados teóricos e da simulação confirmam que íons metálicos ficam retidos no óleo mesmo quando há derrame do óleo na água do mar. / [en] In face of the probability of occurrences of oil spill in marine waters and the lack of information concerning the behavior of the metals in such events, it is necessary to intensify the studies of metal complexes in order to understand the competition between oil ligands and sea water ligands. For such, it is necessary to determine the stability of the complexes formed in oil and compare them with the correspondent ones in sea water. In the present work the binary systems of the complexes of hexanoic acid (a ligand that represents the carboxylic acids of the oil) and 1-propanethiol (which represents the mercaptans) with the metal ions of interest to the petroleum industry - Ni(II), V(IV) and Fe (II) - were studied because they are present in greater quantities. Despite being present in smaller quantities, Cd(II) and Pb(II) were also studied because they are toxic and controlled by environmental organizations. Hexanoic acid has an oxygen atom of the carboxylate group as donor atom, and 1-propanethiol has a sulfur atom of the thiol group. The complexation study was performed in solution using potentiometric titration and ultraviolet-visible spectrophotometry. The dissociation constants of the ligands and the formation constants of the complex species ML, ML2, ML3, MLOH, ML(OH)2, ML(OH)3, ML2OH, ML2 (OH)2 and ML3(OH) were calculated. The values of the stability constants can be divided in two groups: one with the binary complexes of hexanoic acid and the other with the binary complexes of 1-propanethiol. Among the complexes formed with hexanoic acid, the ML species with metal ion Pb(II) was the most stable. In the system of the complexes with 1-propanethiol, the ML species with Cd(II) was the most stable. In the species distribution as a function of pH including the representative ligands of oil and sea water, it could be observed that at pH =7 the most stable species for the metal ions V(IV), Ni(II) and Fe (II) were those with hexanoic acid. In relation to ion Pb(II) the complex formed was with 1- propanethiol. Cd(II), this pH occurred the formation of a small proportion of the complex with 1-propanethiol and a higher percentual (60 percent) of the complexes with the chloride and sulfate íons of sea water. Since the concentration of Cd(II) is in the range of ppb, this metal ion is less relevant when pollution is concerned. Thus, if the monodentate oil ligands studied in this work preferably bind metal ions rather than sea water ligands, than this certainly happens with the polydentate oil ligands such as porphyrins. Using the ultraviolet-visible spectrophotometry technique it was possible to observe the charge transfer bands and the d-d bands. A simulation of oil dispersion was also performed and the concentration of the metals was measured at various times. Both theoretical and simulation data showed that the metal ions are retained in the oil, even when the oil is spread in sea water.

Densification and submergence of floating crude oil is proposed as a novel oil spills treatment method. Surface application of dry granular materials (e.g., quartz sand, limestone) on top of a floating oil layer increases the density of the floating oil phase/granule mixture and leads to formation of relatively large and stable aggregates with significant amounts of captured oil. The aggregates separate from the floating hydrophobic phase and settle by gravity. Implementation of this method will reduce the impact radius of a spill and its mobility, preventing direct contamination of beaches, coastal flora and fauna. The major objective of this research was to examine interactions of particles with hydrophobic liquid-water interface from different perspectives. The important characteristics of the process, such as oil removal efficiencies, optimal particle-to-oil ratios and particle size ranges, were experimentally defined. A series of experiments was conducted to investigate aggregation and dissolution rate constants of the submerged hydrophobic liquids in salt water and deionized water, and to study the impact of the surface porosity of the granular particles on oil capture efficiencies. In addition to crude oil (South Louisiana crude, MC 252), aggregation volumes of quartz sand with other hydrophobic liquids (alkanes and aromatics) were analyzed in relation to wetting characteristics and physical properties of the liquids. A classification of the main types of oil-particle aggregates was developed based on the formation characteristics of the aggregates. Moreover, under specific conditions, depending on the application rates of the granular materials, unique interactions of the particles with the hydrophobic liquid-water interface were observed and defined (bowl formation and roping). These concepts can be utilized to control surface mobility of floating oils, especially during the initial stages of an oil spill, while the oil layer is intact, and when other treatment methods may not be suitable near coastal areas, where transport of floating oils can significantly impact coastal ecosystems.

No description available.

This paper's objective is to determine the best approaches for clean-up of an underground oil leak using cost-benefit analysis. The background aspects of the leak, including a description and history of the oil plume, aspects of the site, and applicable Federal and local regulations, are discussed. Several remediation methods are chosen for examination. The costs associated with each method are estimated. An analysis of the area's property value data using the hedonic approach to benefits estimation is also conducted. Costs of the clean-up of the oil plume are compared to the benefits. It was determined that the amount of estimated benefits from restoration programs is $7.6 million. Based on this information and the cost data, the microbial fence / hydraulic containment method and the enhanced groundwater extraction / hydraulic containment method should be considered as remediation approaches. / Master of Arts

This study was conducted to measure the reduction in polycyclic aromatic hydrocarbons (PAHs) content in oil sludge by co-composting the sludge with pig, cow, horse and poultry manures under laboratory conditions. Four kilograms of soil spiked with 800g of oil sludge was co-composted differently with each manure in a ratio of 2:1 (w/w) spiked soil: manure and wood-chips in a ratio of 2:1 (w/v) spiked soil: wood-chips. Control was set up similar as the one above but without manure. Mixtures were incubated for 10 months at room temperature. Compost piles were turned weekly and moisture level was maintained at between 50% and 70%. Moisture level, pH, temperature, CO2 evolution and oxygen consumption were measured monthly and the ash content at the end of experimentation. Bacteria capable of utilizing PAHs were isolated, purified and characterized by molecular techniques using polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE), amplification of the 16S rDNA gene using the specific primers (16S-P1 PCR and 16S-P2 PCR) and the amplicons were sequenced. Extent of reduction of PAHs was measured using automated soxhlet extractor with Dichloromethane as the extraction solvent coupled with gas chromatography/mass spectrometry (GC/MS). Temperature did not exceed 27.5OC in all compost heaps, pH ranged from 5.5 to 7.8 and CO2 evolution was highest in poultry manure at 18.78μg/dwt/day. Microbial growth and activities were enhanced. Bacteria identified were Bacillus, Arthrobacter and Staphylococcus species. Results from PAH measurements showed reduction between 77 and 99%. The results from the control experiments may be because it was invaded by fungi. Co-composting of spiked soils with animal manures enhanced the reduction in PAHs. Interestingly, all bacteria isolated and identified in this study were present in all treatments, including the control. / Environmental Sciences / M.Sc. (Environmental Sciences)