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Photo-Enhanced Toxicity of Oil Constituents and Corexit 9500 to Gulf of Mexico Marine Organisms

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Photo-Enhanced Toxicity of Oil Constituents and Corexit 9500 to Gulf of Mexico Marine Organisms AN ABSTRACT OF THE DISSERTATION OF Bryson E. Finch for the degree of Doctor of Philosophy in Toxicology presented on December 11, 2015. Title: Photo-enhanced Toxicity of Oil Constituents and Corexit 9500 to Gulf of Mexico Marine Organisms Abstract approved: ______________________________________________________________________________ William A. Stubblefield Significant inputs of hydrocarbons are continually released into the environment from anthropogenic and natural sources. Some of the most toxic hydrocarbon compounds are polycyclic aromatic hydrocarbons. Polycyclic aromatic hydrocarbons are known for their ability to absorb ultraviolet light and enhance toxicity. Generally, PAHs exert their toxicity via narcosis but UV-absorbing PAHs can become photosensitized and significantly exacerbate toxic effects. During crude oil spills, PAHs are released in large amounts that have potential for narcotic and phototoxic effects on aquatic organisms. As a result of the Deepwater Horizon oil spill, effort was placed on quantifying toxic effects of crude oils and oil constituents for aquatic organisms. The following studies attempted to characterize narcotic and phototoxic effects that may have occurred during the Deepwater Horizon incident; however, the results of this research are equally applicable to any PAH exposure scenario. The objectives of the following studies were to: 1) identify susceptible stages of Gulf of Mexico organisms to the photo-enhanced toxicity of PAHs, 2) determine the importance of UV intensity and exposure duration on phototoxicity, 3) determine the effect of alkylation on the phototoxic potency of PAHs, 4) validate the assumption of additivity for phototoxic PAHs mixtures, 5) evaluate the potential for narcotic toxicity and phototoxicity of fresh and weathered Macondo crude oils released from the Deepwater Horizon, and 6) assess the potential for ongoing oil phototoxicity at field sites in the Gulf of Mexico. Model organisms used in studies included the mysid shrimp (Americamysis bahia), inland silverside (Menidia beryllina), sheepshead minnow (Cyprinodon variegatus), and Gulf killifish (Fundulus grandis). Studies demonstrated that organism sensitivity to phototoxicity of PAHs decreased with organism age and increasing pigmentation. Photo-enhanced toxicity was, to some extent, dependent on the degree of organism pigmentation. Generally, high-intensity short- duration UV treatments resulted in greater toxicity than low-intensity long-duration UV treatments at similar UV doses. Fresh Macondo crude oil was more toxic than weathered crude oils, both in the presence and absence of UV light. Differences in toxicity between fresh and weathered crude oils were primarily attributed to the lighter mono and di-aromatic hydrocarbons in fresh crude oils. Phototoxic PAH concentrations were relatively similar among fresh and weathered crude oils, suggesting recalcitrance to oil weathering processes. The addition of Corexit 9500, an oil-dispersant used during the Deepwater Horizon oil spill, to crude oil in laboratory experiments increased toxicity compared to tests conducted with crude oil alone. It is anticipated that this enhanced response resulted from the increased concentrations of phototoxic and narcotic PAHs in water-accommodated fractions and the inherent toxicity of Corexit 9500. Weathered crude oil present in previously heavily-oiled Barataria Bay, LA field sites was found to pose little or no phototoxic risk in ambient environmental conditions four years after the Deepwater Horizon oil spill. Water-accommodated fractions of field-collected oil suggest slight phototoxic potential to mysid shrimp in the laboratory in highly transparent artificial seawater. When examining mixtures of phototoxic PAHs in crude oil, laboratory studies suggested that toxicity adhered to an “additive interactions” model; therefore, predictive toxicity models should consider an additivity model for assessing the toxicity of hydrocarbon mixtures. Furthermore, PAH phototoxic potency seemed to increase with increasing methylation for all phototoxic PAHs examined. In fact, phenanthrene, a non-phototoxic PAH, demonstrated a slight degree of phototoxicity when methylated. Overall, predictive models based on HOMO-LUMO gap were relatively accurate in predicting phototoxicity compared with empirical data generated in the present study. Future models should consider effects of other substituents on photo-enhanced toxicity of PAHs due to toxicity differences between unsubstituted and alkylated PAHs observed in the present studies. Data presented in this dissertation, can be used in part, as the basis for an ecological risk assessment for the photo-enhanced toxicity of oil constituents in the Gulf of Mexico during the Deepwater Horizon oil spill. ©Copyright by Bryson E. Finch December 11, 2015 All Rights Reserved Photo-enhanced Toxicity of Oil Constituents and Corexit 9500 to Gulf of Mexico Marine Organisms By Bryson E. Finch A DISSERTATION submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Presented December 11, 2015 Commencement June 2016 Doctor of Philosophy dissertation of Bryson E. Finch presented on December 11, 2015. APPROVED: Major Professor, representing Toxicology Head of the Department of Environmental and Molecular Toxicology Dean of the Graduate School I understand that my dissertation will become part of the permanent collection of Oregon State University libraries. My signature below authorized release of my dissertation to any reader upon request. Bryson E. Finch, Author ACKNOWLEDGEMENTS The author expresses his sincere appreciation to several coauthors including William Stubblefield, Solmaz Marzooghi, and Dominic Di Toro. The coauthors were instrumental in the planning and development of studies. A special thanks is deserved to my advisor William Stubblefield for the opportunity to work in the aquatic toxicology laboratory at Oregon State University, his mentorship, and advice. Special gratitude goes out to my committee members, Jeffrey Jenkins, Chris Langdon, Dave Stone, and James Hermes for their time, effort, and advice as I progressed through my program of study. The author would also like to commend British Petroleum associates and consultants, Piero Gardinali and Adolfo Fernandez for chemical analyses, Aaron Edgington for his advice, Paul Toll and Allison Cardwell for quality assurance, and Matthew Sroufe and Warren Hanson for their laboratory assistance. Alan Jones, Brittany Honisch, and Michael Brown were instrumental in conducting field studies. I would like to thank my family for their support and patience through my graduate studies, especially my wife and daughter. Partial funding for this project was provided by BP Exploration & Production Inc. Project findings and conclusions are those of the authors alone, and may not reflect the views of BP. CONTRIBUTION OF AUTHORS Dr. William Stubblefield assisted in the procurement of funding, design, interpretation of data, and advisement. Solmaz Marzooghi and Dr. Dominic Di Toro were instrumental in the selection of phototoxic PAHs for use in studies and study design. TABLE OF CONTENTS PAGE Chapter 1: Introduction ................................................................................................................... 1 1.1 Background ............................................................................................................................................. 1 1.2 References ............................................................................................................................................... 8 Chapter 2: Photo-enhanced Toxicity of Fluoranthene to Gulf of Mexico Marine Organisms at Different Larval Ages and Ultraviolet Light Intensities ............................................................... 12 2.1 Introduction ........................................................................................................................................... 12 2.2 Methods ................................................................................................................................................. 15 2.2.1 Animal care and use ....................................................................................................................... 15 2.2.2 Experimental design ....................................................................................................................... 16 2.2.3 Photoperiod .................................................................................................................................... 17 2.2.4 Age sensitivity studies ................................................................................................................... 17 2.2.5 Intensity studies ............................................................................................................................. 18 2.2.6 Pigmentation .................................................................................................................................. 18 2.2.7 Chemical analysis .......................................................................................................................... 19 2.2.8 Statistical analysis .......................................................................................................................... 20 2.3 Results ..................................................................................................................................................
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