Made available in DSpace on 2016-06-02T19:28:57Z (GMT). No. of bitstreams: 1 TeseMVR.pdf: 1800586 bytes, checksum: c44cb463d61ffeb5394f543684f66e59 (MD5) Previous issue date: 2003-06-24 / Concern with the effect of oil spills in coastal regions resulting from the production, refining and transport of this product has been one of the priorities of the institutions working with this sector. Consequently, there is a large demand for research on the impacts of by accidents on the environment and, particularly, on natural communities. In the present study, a mesocosm experiment was used to evaluate the effects of a mixture of light Arabian and Russian oil with the chemical dispersant Corexit® 9500, over a coastal plankton community. The experiment was carried out in Rio de Janeiro and lasted 25 consecutive days. Three replicates were used as control, with only seawater, three were treated with 800 mL of petroleum and the other three were treated with the mixture 800 mL of petroleum and 80 mL of dispersant. The chemical alterations in the water were striking, especially the rise in the concentration of organic compounds. The results demonstrated a severe reduction of phytoplankton density, as a result of the addition of oil. There was also a change in the composition of the organism groups, with alteration of dominance of diatoms to phytoflagelates. Similar effect was found for the zooplankton. Both the oil and its mixture with dispersant resulted in a reduction of population densities and changes, or disappearance, of some components. Meroplanktonic organisms had a higher sensitivity to the acute effects of the oil and oil-dispersant mixture than holoplanktonic organisms. Copepods were resistant to the effects of oil and oil-dispersant mixture. Among the herbivores, Acartia lilljeborgi had greater resistance to the acute toxic effect of oil, whereas Pseudodiaptomus acutus was more resistant to the chronic effects of both oil and the mixture. Among carnivores, Oithona hebes appeared as a resistant species to both acute and chronical effects. Mesocosms were shown to be useful for investigating the effects of oil spills on marine environments since standardized laboratory tests with algae and invertebrate test-organisms corroborated the field findings. / A avaliação dos efeitos de derrames de petróleo nas regiões costeiras decorrentes das atividades de produção, refinamento ou transporte deste produto tem sido uma das prioridades das instituições ligadas a este setor e há uma demanda muito grande de pesquisas sobre os impactos ocasionados por estes sobre o ambiente e as comunidades naturais, em particular. No presente estudo a experimentação em mesocosmos foi utilizada para avaliar os efeitos do derrame do petróleo ARLE/URAL e deste tratado com o dispersante químico Corexit® 9500, sobre uma comunidade planctônica costeira. O experimento foi realizado no Rio de Janeiro, Brasil e teve a duração de 25 dias consecutivos (19/06 a 13/07/2002). Os tratamentos foram feitos em triplicata com um volume aproximado de 1,7m3 de água do mar em cada unidade. Foram utilizadas três réplicas como controle, contendo apenas água do mar, três réplicas foram tratadas com 800 mL de petróleo e três outras réplicas foram tratadas com a mistura de 800 mL de petróleo e 80 mL de dispersante. As alterações químicas na água foram marcantes, principalmente em relação ao aumento na concentração dos compostos orgânicos. Os resultados evidenciaram uma redução severa na densidade do fitoplâncton, em decorrência da adição do óleo ou da mistura de óleo e dispersante. Houve também uma mudança na composição dos grupos, com alteração da dominância de diatomáceas para fitoflagelados. Em relação aos grupos zooplanctônicos também foi observado um efeito mais acentuado no tratamento com petróleo e dispersante. Os organismos meroplanctônicos foram mais sensíveis ao petróleo do que os holoplanctônicos. Os copépodes foram dominantes, em todos os tratamentos. A espécie herbívora Acartia lilljeborgi foi mais resistente ao efeito agudo do petróleo, enquanto Pseudodiaptomus acutus foi mais resistente ao efeito crônico Entre os Copepoda carnívoros Oithona hebes foi a espécie mais resistente, tanto ao impacto agudo quanto ao impacto crônico. Os mesocosmos são adequados para a avaliação dos efeitos do derrame de petróleo ou da mistura de petróleo e dispersante, como corroborado pelos estudos de toxicidade com algas e organismos-teste invertebrados, que corroboraram os efeitos observados em campo. A utilização de dispersante químico na etapa de remediação após os derrames necessita ser reavaliada tendo em vista os resultados deste trabalho que indicam que a mistura petróleodispersante é ainda mais tóxica do que o petróleo sozinho.

The development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging contaminants, the detection and quantification of chemicals used in unprecedented quantities and applications, and the extraction of compounds from complex matrices where the solvent-solute-matrix interactions are not completely understood. The three studies present analytical methods developed for emerging contaminants in complex matrices, including: fluorochemical surfactants in aqueous film-forming foams, oil dispersant surfactants in seawater, and fullerene nanomaterials in carbonaceous solids. Aqueous film-forming foams, used in military and commercial firefighting, represent environmentally-relevant commercial mixtures that contain a variety of fluorochemical surfactants. Combining the surfactant-selective ionization of fast atom bombardment mass spectrometry with high resolution mass spectrometry, chemical formulas for 11 different fluorochemical classes were identified. Then AFFF-related patents were used to determine the structures. Of the eleven classes of fluorochemicals, ten have little, if any, data on their environmental occurrence, fate, and potential impacts in the peer-reviewed literature. In addition, nine of the identified classes had either cationic or zwitterionic functionalities and are likely to have different transport properties compared to the well-studied anionic fluorochemicals, such as perfluorooctanoate. After the Deepwater Horizon oil spill in the summer of 2010, one of the emergency response methods for the mitigation of the oil's environmental impact was the use of unprecedented amounts of oil dispersant to break down the oil slick and encourage biodegradation. This event illustrated the need for rapid analytical method development in order to respond to the potential environmental disaster in a timely manner. Using large volume injection liquid chromatography with tandem mass spectrometry, an analytical method was developed for the trace analysis of the multiple dispersant surfactant classes and the potential degradation products of the primary surfactant. Limits of detection ranged from 49 ��� 3,000 ng/L. The method provided excellent recovery (86 ��� 119%) and precision (10 ��� 23% RSD), while also accommodating for the high salinity of seawater samples and analyte contamination. Despite the fact that fullerene nanomaterials have been studied for almost three decades, research is still being conducted to fully understand the environmental properties of these materials. Previous studies to extract fullerenes from environmental matrices have resulted in low efficiency, high variability, or the extraction efficiencies have gone unreported. Extraction by ultrasonication with toluene and 1-methylnaphthalene increased the recovery 5-fold of a spiked, isotopically-labeled C������ surrogate from carbon lampblack as compared to that of the conventional approach of extracting with 100% toluene. The study revealed the importance of evaluating experimental variables such as extraction solvent composition and volume, and sample mass, as they have a significant impact on the quantitative extraction of fullerenes from environmental matrices. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Aug. 15, 2012 - Aug. 15, 2013