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Photochemical Transformation of Three Polycyclic Aromatic Hydrocarbons, Ibuprofen, and Caffeine in Natural Waters

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Photochemical Transformation of Three Polycyclic Aromatic Hydrocarbons, Ibuprofen, and Caffeine in Natural Waters PHOTOCHEMICAL TRANSFORMATION OF THREE POLYCYCLIC AROMATIC HYDROCARBONS, IBUPROFEN, AND CAFFEINE IN NATURAL WATERS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor Philosophy in the Graduate School of The Ohio State University By Laura Elizabeth Jacobs, M.S. The Ohio State University 2008 Approved by _____________________________________ Dissertation Committee: Advisor Professor Yu-Ping Chin, Advisor Approved by Professor Linda K. Weavers _____________________________________ Professor Terry L. Gustafson Advisor Professor Harold Walker Environmental Science Graduate Program Copyright Laura Elizabeth Jacobs 2008 ABSTRACT The photolysis of three polycyclic aromatic hydrocarbons (PAHs), pyrene, phenanthrene, and naphthalene were studied in waters taken from Gary, Indiana (GIN) and Wilmington, North Carolina (WNC). Direct photolysis of PAHs was observed with pyrene degrading at a faster rate than either phenanthrene or naphthalene. When compared to direct photolysis, phenanthrene degradation increased in GIN water, but decreased in the WNC water due to higher levels of dissolved organic carbon (DOC) for WNC (9.29 mg/L vs 6.73 mg/L for GIN) and less nitrate (0.046 mM vs 0.205 mM) for GIN. The slightly lower rate of phenanthrene degradation in WNC water, corrected for light attenuation effects, is statistically the same as the direct photolysis experiments. We attribute the lower rate of degradation in the presence of WNC water to light screening by DOC, while we believe that the faster reaction rate observed for GIN is the result of nitrate generated hydroxyl radical (OH•) chemistry. Overall photo-reaction rates decrease for the lower molecular weight PAHs as the fastest naphthalene photolytic rate was roughly two orders of magnitude slower than the photolysis of pyrene. The photolysis of ibuprofen and caffeine was studied in solutions of fulvic acid isolated from Pony Lake, Antarctica (PLFA); Suwannee River, GA (SRFA); and Old Woman Creek Natural Estuarine Research Reserve, OH (OWCFA). At 10µM initial concentration ibuprofen and caffeine degrade slowly by direct photolysis, but we ii observed enhanced photodegradation in solutions of each fulvic acid. Quenching studies suggest OH• plays a prominent role in both caffeine and ibuprofen photolysis. Spectroscopic techniques reveal the formation of multiple hydrophobic photo-products upon photolysis of ibuprofen, the dominant byproduct identified as 1-(4- isobutylphenyl)ethanol and a minor derivative isobutylacetophenone. Caffeine and ibuprofen photolysis reactions proceed even more quickly in fulvic acid solutions (6 mg/L DOC) at lower, more environmentally relevant concentrations (0.1 µM) where presumably reaction kinetics are controlled by both short and long lived reactive species. When probing the responsible reactive transients under suboxic conditions, fulvic acid mediated photolysis of caffeine and ibuprofen slows suggesting the influence of an oxygen dependent long lived radical (peroxyl or phenoxyl radicals) playing a role at 0.1µM. iii DEDICATION To Chris. For Dad. iv ACKNOWLEDGMENTS I would like to thank my advisors Yu-Ping Chin and Linda K. Weavers for their belief my abilities. It has been a pleasure working with them both over the past four years. A special thanks to Ryan L. Fimmen and Heath Mash. Both the ibuprofen work and my education would not be what it is without their input and patience. I thank the additional members of my PhD committee for their intellectual support, Terry L. Gustafson and Harold Walker. For technical support I thank Tanya Young and Kathy Welch. For unlimited field assistance I thank Old Woman Creeks senior research scientist Dave Klarer. Additional colleagues providing intellectual support include Kristopher McNeill, Eric Weber, Beate Escher, Richard Zepp, Silvio Canonica, William J. Cooper and Kristin Schirmer. Additionally, I am indebted to the Chin and Weavers Research Groups, whose support, friendship, and collaboration made this undertaking possible. Most importantly, I would like to thank Chris, my father, mother, sister, and Ale. I love each of you dearly. Finally, I would like to thank the sponsors of this research: National Science Foundation Grant BES-0504434 and NOAA’s National Estuarine Research Reserve System Graduate Research Fellowship (Laura E. Jacobs). v VITA B.A. Geology, Clemson University…………………………………...………………2000 M.S. Geology, Vanderbilt University…………………………………………………2003 Graduate Research Associate, The Ohio State University……………….……..2004-2005 Graduate Research Fellow, The Ohio State University………………………...2005-2008 FIELD OF STUDY Major Field: Environmental Science vi TABLE OF CONTENTS Page Abstract……………………………………………………………………..……… ii Dedication………………………………………………………………………….. iv Acknowledgements………………………………………………………………… v Vita…………………………………………………………………………………. vi List of Tables………………………………………………………………………. x List of Figures……………………………………………………………………… xi Chapters: 1. Introduction……………………………………………………………………… 1 1.1 Nature of Scope of Research…………………………………………… 1 1.2 Photochemistry in Natural Waters……………………………………… 2 1.3 Dissolved Organic Matter………………………………………………. 5 1.4 Objectives of This Dissertation………………………………………… 7 1.5 References……………………………………………………………… 9 1.6 Figures…………………………………………………………………. 12 2. Direct and Indirect Photolysis of Polycyclic Aromatic Hydrocarbons in Nitrate-rich Surface Waters………………………………………………………... 15 2.1 Introduction…………………………………………………………….. 15 2.2 Methods………………………………………………………………… 18 2.2.1 Materials……………………………………………………... 18 2.2.2 Photolytic Reactions…………………………………………. 18 2.3 Results and Discussion…………………………………………………. 20 2.4 Conclusions…………………………………………………………….. 27 2.5 References……………………………………………………………… 29 2.6 Tables…………………………………………………………………... 32 vii 2.7 Figures…………………………………………………………………. 33 3. Ibuprofen Photolysis in the Presence of Three Fulvic Acids…………………… 38 3.1 Introduction……………………………………………………………. 38 3.2 Methods……………………………………………………………….. 41 3.2.1 Chemicals and Fulvic Acids…………………………………. 41 3.2.2 Photolytic Reactions………………………………………… 41 3.2.3 Natural Sunlight Experiment………………………………... 43 3.2.4 HPLC……………………………………………………….. 43 3.3 Results and Discussion………………………………………………... 44 3.3.1 10 µM Photolysis Experiments……………………………… 44 3.3.2 0.1 µM Photolysis Experiments…………………………….. 47 3.4 Conclusions………………………………………………………….... 49 3.5 References…………………………………………………………….. 51 3.6 Tables…………………………………………………………………. 53 3.7 Figures………………………………………………………………… 54 4. Ibuprofen Photolysis: A Byproduct Analysis and Proposed Chemical Mechanism……………………………………………………………………….. 59 4.1 Introduction………………………………………………………….... 59 4.2 Methods……………………………………………………………….. 60 4.2.1 Chemicals………………………………………………..….. 60 4.2.2. Photolytic Reactions……………………………………….. 61 4.2.3 LC-MS…………..………………………………………….. 61 4.3.4 GC-MS……………………………………………………... 59 4.3.5 1H and COSY NMR………………………………………... 62 4.3 Results and Discussion………………………………………………… 63 4.4. Conclusion…………………………………………………………… 67 4.5 References……………………………………………………………. 68 4.6 Tables…………………………………………………………………. 69 4.7 Figures………………………………………………………………… 70 4.8 Schemes……………………………………………………………….. 81 5. Caffeine as a Wastewater Tracer: A Photochemical Analysis………………… 82 5.1 Introduction…………………………………………………………… 82 5.2 Methods………………………………………………………………. 85 5.1.1 Materials……………………………………………………. 85 5.2.2. Photolytic Reactions……………………………………….. 86 5.3 Results and Discussion……………………………………………….. 87 5.4 Conclusion……………………………………………………………. 92 5.5. References……………………………………………………………. 94 5.6 Figures………………………………………………………………… 97 6. Conclusions and Future Research……………………………………………… 103 viii 6.1 Conclusions…………………………………………………………. 103 6.2 Future Research…………………………………………………….. 107 Bibliography……………………………………………………………………. 109 Appendices…………………………………………………………………….. 117 A. Chemical Actinometry…………………………………………….... 117 A.1 Solar Simulator Chemical Actinometry……………………. 117 A.2 Natural Photolysis Chemical Actinometry……………….... 121 ix LIST OF TABLES Table Page 2.1 Selected Gary, Indiana (GIN) and Wilmington, North Carolina (WNC) - water parameters (dissolved organic carbon (DOC), nitrate (NO3 ), total -1 iron (Fe)) and observed photolytic degradation rate constants (kobs h ) in Milli-Q water and our samples; (-) Denotes not applicable………………….. 32 3.1 10 µM and 0.1 µM racemic and S-(+) (when indicated) ibuprofen -1 degradation rate constants (kobs h ) in the presence of simulated and natural sunlight, OWCFA (Old Woman Creek Fulvic Acid), SRFA (Suwannee River Fulvic Acid), and PLFA (Pony Lake Fulvic Acid) at indicated dissolved organic carbon levels (DOC), in the absence of molecular oxygen, and in the presence of isopropanol. (–) Denotes not applicable…………… … 53 4.1 Gas Chromatography-Mass Spectrometry (GC-MS) dominant ion peaks (1-11) from 10 µM ibuprofen solution photolyzed 48 h confirming the presence of numerous byproducts in solution, several mw ~176. (-) Denotes not applicable………………………………………………………………. … 69 x LIST OF FIGURES Figure Page 1.1 Illustration of the dissolved organic matter source continuum using the two end members Suwannee River Fulvic Acid (SRFA) and Pony Lake Fulvic Acid (PLFA); and Old Woman Creek Fulvic Acid (OWCFA)……… 12 1.2 Aerial photo of Old Woman Creek National Estuarine Research Reserve, Huron, OH. Courtesy of Dave Klarer……………………………………….. 13 1.3 Chemical structures of chosen non-point source contaminants…………….. 14 2.1 Photoinduced degradation of pyrene in Milli-Q and Wilmington, North -1 Carolina (WNC) and Gary, Indiana (GIN) sample waters where kobs h is the observed rate constant
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