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Deepwater Horizon Oil Spill: Using Microcosms to Study Effects Of DEEPWATER HORIZON OIL SPILL: USING MICROCOSMS TO STUDY EFFECTS OF CRUDE OIL IN COASTAL SEDIMENTS by ERIKA KRISTINE RENTSCHLER DR. RONA J. DONAHOE, COMMITTEE CHAIR DR. YUEHAN LU DR. GEOFFREY TICK DR. PATRICIA SOBECKY A THESIS Submitted in partial fulfillment of the requirements for the degree of Master of Science in the Department of Geological Sciences in the Graduate School of The University of Alabama TUSCALOOSA, ALABAMA 2013 Copyright Erika Kristine Rentschler 2013 ALL RIGHTS RESERVED ABSTRACT Approximately 4.9 million gallons of crude oil traveled with ocean currents to reach the Gulf coast after the Deepwater Horizon oil drilling rig explosion. Microcosm experiments were conducted to determine how oil contamination affects the concentration and distribution (between solid and aqueous phases) of trace elements in a salt marsh environment. Sediment and seawater from a salt marsh at Bayou La Batre, Alabama, were measured into jars and spiked with 500 ppm MC-252 oil. The solid phase and aqueous samples were analyzed by ICP-OES, ICP- MS, and IC. A second experiment was conducted using various concentrations (0 ppm, 10 ppm, 100 ppm, 500 ppm, 1000 ppm, 2500 ppm) of MC252 oil. ICP-OES data show variations in aqueous elemental concentrations occurred over the 14 day experiment. The pH for the water in the experiments ranged from 6.93 to 8.06. Significant positive correlations (r>0.75) were found in the solid phase samples between iron and the following elements: aluminum, cobalt, chromium, and nickel. Aqueous iron concentrations were highly correlated (r>0.75) with solution pH. The presence of iron oxide and clays in the salt marsh sediment indicates potential for adsorption of trace elements sourced from the environment and from crude oil contamination. The release of aqueous Fe (II) observed between two and 14 days is likely caused by reductive dissolution of iron-bearing clays or iron oxide. All the samples that contained oil behaved in similar ways with respect to time, but the controls showed almost no changes in the concentrations of the trace elements. Although the levels of some trace elements in the solid phase changed during the experiments, their final concentrations were at the same levels as the control samples. With the exception of nickel, the 14 day samples contained lower trace metal concentrations than the sterile control which contained no oil. The reason for this is likely ii attributable to the in situ oil-degrading bacteria, which were found to be present in the sediment. The oil-degrading bacterial community increased in the presence of oil and decreased as the oil concentration decreased. Oil-degrading bacteria are capable of inducing reductive dissolution in Fe (III) minerals. iii DEDICATION This thesis is dedicated to everyone who helped and guided me through the trials and tribulations of this research. In particular, my husband, my family, and my “fur babies” (Angel, Ninja, and Paytra). You all have been an amazing source of emotional support and encouragement. iv ACKNOWLEDGMENTS I would like to thank Dr. Rona Donahoe for her guidance and for sharing her knowledge of geochemistry. I would like to thank my committee members, Yuehan Lu, Geoff Tick, and Patricia Sobecky for their invaluable input, inspiring questions, and support of both the thesis research and my academic progress. I thank Ghanashyam Neupane (Hari) for showing me how to perform an alkalinity titration, a microwave digestion, and for finding things in the lab for me when I had no idea where to look. I thank Sidhartha Bhattacharyya (Sid) for analyzing my oily samples on the ICP and for teaching me how to arrange the spreadsheets to make sense of all that data. Thank you to Jason Harvell, my husband, for going with me on sampling trips, helping me in the lab when nobody else could, and for bringing me cupcakes when I’m stressed out. Drew Raulerson has been indispensable with his four-wheel drive truck, strong arms, and his willingness to help inside and outside the lab. I thank Whitney Harris for driving 400 miles with me, out of her own curiosity, and for grabbing me for balance in the water that one time, which led to disaster! I thank all of the undergraduate research assistants for the extra hands. This research would not have been possible without the support of my friends and fellow graduate students. I am lucky to have such an amazing support system. Thank you to my family who never stopped encouraging me. You told me I could be whatever I wanted to be and I will always strive to prove you right. v CONTENTS ABSTRACT ................................................................................................ ii DEDICATION ........................................................................................... iv ACKNOWLEDGMENTS ...........................................................................v LIST OF TABLES ................................................................................... viii LIST OF FIGURES ................................................................................... ix 1. INTRODUCTION ...................................................................................1 2. STUDY AREA ........................................................................................8 3. METHODOLOGY ................................................................................11 a. Field Sampling Methods and Materials .....................................11 b. Experimental Design ..................................................................11 c. Laboratory Methods ...................................................................14 4. RESULTS ..............................................................................................18 a. Time Series Major Elements (Aqueous) ....................................18 b. Time Series Minor Elements (Aqueous)....................................20 c. Time Series Trace Elements (Aqueous) .....................................22 d. Time Series Solid Phase Sample Composition ..........................31 e. Concentration Variation Major Elements (Aqueous) ................36 f. Concentration Variation Minor Elements (Aqueous) .................39 g. Concentration Variation Trace Elements (Aqueous) .................40 h. Concentration Variation Solid Phase Sample Composition ......42 i. Geochemical modeling ...............................................................45 vi 5. DISCUSSION ........................................................................................49 6. CONCLUSION ......................................................................................55 REFERENCES ..........................................................................................57 APPENDIX I .............................................................................................60 APPENDIX II ............................................................................................72 vii LIST OF TABLES Table 1. Time Series Experiment Design ..................................................10 Table 2. Concentration Variation Experiment Design ...............................11 Table 3. Time Series Major Element Chemistry (aqueous) .......................17 Table 4. Time Series Major Element Chemistry (aqueous), cont. .............17 Table 5. Time Series Minor Element Chemistry (aqueous) ......................18 Table 6. Time Series Trace Element Chemistry (aqueous) .......................19 Table 7. Time Series Trace Element Chemistry (aqueous), cont. .............20 Table 8. Regression results of Time Series trace elements ........................29 Table 9. Concentration Variation Major Element Chemistry (aqueous) ...35 Table 10. Concentration Variation Major Element Chemistry (aqueous), cont. ...........................................................................................36 Table 11. Concentration Variation Minor Element Chemistry (aqueous) .37 Table 12. Concentration Variation Trace Element Chemistry (aqueous) ..38 Table 13. Regression results of Concentration Variation trace elements ..40 Table 14. Trace metals found in salt marshes in South Carolina (Sanger et al., 1999) and trace metal averages for Time Series Experiment sediment ................................................................50 viii LIST OF FIGURES Figure 1. Transformation of Fe (II, III) at an oxic-anoxic boundary in a water or sediment column .............................................................4 Figure 2. Main principle of aerobic degradation of hydrocarbons by microorganisms .............................................................................5 Figure 3. Location of Bayou La Batre .........................................................9 Figure 4. Aerial View of Sample Site Location .........................................10 Figure 5. Trend in iron concentration for Time Series Experiment aqueous samples.........................................................................21 Figure 6. Trend in copper concentration for Time Series Experiment aqueous samples.........................................................................24 Figure 7. Trend in nickel concentration for Time Series Experiment aqueous samples.........................................................................25 Figure 8. Trend in zinc concentration for Time Series Experiment aqueous samples.........................................................................26 Figure 9. Trend in vanadium concentration for Time Series Experiment aqueous samples.........................................................................27
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