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Photochemistry of Polycyclic Aromatic Hydrocarbons with Environmentally Relevant Metals

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Photochemistry of Polycyclic Aromatic Hydrocarbons with Environmentally Relevant Metals University of Denver Digital Commons @ DU Electronic Theses and Dissertations Graduate Studies 1-1-2018 Photochemistry of Polycyclic Aromatic Hydrocarbons with Environmentally Relevant Metals John P. Haynes University of Denver Follow this and additional works at: https://digitalcommons.du.edu/etd Part of the Analytical Chemistry Commons, and the Environmental Chemistry Commons Recommended Citation Haynes, John P., "Photochemistry of Polycyclic Aromatic Hydrocarbons with Environmentally Relevant Metals" (2018). Electronic Theses and Dissertations. 1436. https://digitalcommons.du.edu/etd/1436 This Dissertation is brought to you for free and open access by the Graduate Studies at Digital Commons @ DU. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons @ DU. For more information, please contact [email protected],[email protected]. Photochemistry of Polycyclic Aromatic Hydrocarbons with Environmentally Relevant Metals __________ A Dissertation Presented to the Faculty of Natural Sciences and Mathematics University of Denver __________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy __________ by John P. Haynes June 2018 Advisor: Brian J. Majestic Author: John P. Haynes Title: Photochemistry of Polycyclic Aromatic Hydrocarbons with Environmentally Relevant Metals Advisor: Brian J. Majestic Degree Date: June 2018 ABSTRACT The details of the work presented in this dissertation focus on simulated reactions in the atmosphere and water systems between persistent aromatic compounds and varying species of metals with an emphasis on iron. Bulk water suspensions of a standard soil and polycyclic aromatic hydrocarbons (PAH) were analyzed for soluble iron by inductively- coupled plasma mass spectroscopy (ICP-MS) following a 16 hour reaction period using simulated sunlight. Significant increases in soluble iron were only seen with 2-3 ring linear PAH and carboxylic acids. A two-stage study was conducted to investigate the potential for and possible mechanisms involving the photo-oxidation of PAH into humic-like substances (HULIS). Aqueous suspensions of PAH and oxidized PAH products are illuminated by a bench solar simulator and resulting samples are analyzed by high-pressure liquid chromatography (HPLC), UV-Vis, attenuated total reflectance Fourier transformer infrared spectroscopy (ATR-FTIR), solid-phase extraction (SPE), and electrospray ionization/atmospheric pressure chemical ionization mass spectroscopy (ESI/APCI-MS). HULIS production is based on comparison to SRFA and is observed in short chain PAH following a surface dependent path through naphthalene derivative intermediate structures. These results help explain brown carbon and health effects observed in areas affected by urban emissions. ii ACKNOWLEDGEMENTS I would like to take this time to give a very special thank you to my advisor and mentor Dr. Brian J Majestic. I very much appreciate the time, patience, and understanding that you have given to help me grow as a scientist. A very special thanks is also given to my co-advisor Dr. Keith Miller, whose guidance has always proven very helpful, and the other members of my committee, Drs. Alex Huffman and Shannon Murphy. My great appreciation also goes out to the many University of Denver faculty members who have offered their time and advice for me and my many constant questions. Thank you very much to Dr. Michelle Knowles, Dr. Todd Wells, Dr. Bryan Cowen, Dr. Gary Bishop, and Dr. John Latham. I would also like to acknowledge my appreciation for the University of Denver and the National Science Foundation for their funding and support over my time here. I would also extend my warm regards and special thanks to the undergraduates. Thank you very much to Eva Cutler, Elizabeth Kepl, and Sarah McDonald. A very special thank you and gratitude to all of my friends and cohorts for your support and words of encouragement! Thanks to my fellow project members Dr. Benton Cartledge, Dr. Nitika Dewan, Molly Haugen, Joe Salazar, Rachel Marini, and Heather Runberg. And to everyone to whom we could lean on for support: Michael Holden, Emily Hager, Amani Alhalwani, Taylor Firman, and Ben Swanson. And, of course, thank you to my family both near and far for your support. iii TABLE OF CONTENTS Chapter One: Introduction .................................................................................................. 1 1.1 Persistent Pollutants .......................................................................................... 1 1.2 HULIS and Humic Character............................................................................ 2 1.3 Environmentally Relevant Iron Species............................................................ 3 1.4 Reactive Oxygen Species .................................................................................. 4 1.5 Radical Generating Environments .................................................................... 4 1.6 Analytical Techniques ...................................................................................... 5 Chapter Two: Role of Polycyclic Aromatic Hydrocarbons on the Photo-catalyzed Solubilization of Atmospheric Iron .................................................................................... 7 2.1 Abstract ............................................................................................................. 7 2.2 Introduction ....................................................................................................... 8 2.3 Experimental ................................................................................................... 12 2.4 Results ............................................................................................................. 18 2.5 Discussion ....................................................................................................... 31 2.6 Conclusions ..................................................................................................... 40 Chapter Three: Photo-induced Auto-oxidation of Polycyclic Aromatic Hydrocarbons Resulting in Humic-like Substance Production ................................................................ 41 3.1 Abstract ........................................................................................................... 41 3.2 Introduction ..................................................................................................... 41 3.3 Experimental ................................................................................................... 46 3.4 Results ............................................................................................................. 49 3.5 Discussion ....................................................................................................... 58 Chapter Four: Investigation into Humic-like Substance Production via Aqueous Photo- oxidation of Polycyclic Aromatic Hydrocarbons ............................................................. 62 4.1 Abstract ........................................................................................................... 62 4.2 Introduction ..................................................................................................... 62 4.3 Experimental ................................................................................................... 68 4.4 Results ............................................................................................................. 72 4.5 Discussion ....................................................................................................... 83 4.6 Conclusions ..................................................................................................... 94 Chapter Five: Summary and Future Work ........................................................................ 96 References ....................................................................................................................... 101 Appendix A ..................................................................................................................... 116 Appendix B ..................................................................................................................... 119 iv LIST OF FIGURES Figure 2. 1: Soluble iron as a percent of total iron in photoreaction samples................... 20 Figure 2. 2. Iron response as a ratio of percent soluble iron in light. ............................... 22 Figure 2. 3. Difference in average ppb concentrations of soluble metals. ........................ 24 Figure 2. 4. Acidity of unbuffered PAH samples with soil. ............................................. 27 Figure 2. 5. Comparison of dissolved organic reagents and resulting solubilized iron. ... 30 Figure 3. 1: UV-vis analysis of saturated suspensions of PAH. ....................................... 51 Figure 3. 2: HPLC analysis of post-reaction samples of saturated PAH. ......................... 53 Figure 3. 3: ATR-FTIR analysis of NAP and ANT products. .......................................... 55 Figure 3. 4: Solid phase extraction spectra of UV-vis and HPLC data. ........................... 57 Figure 4. 1: Structures of PAH and oxPAH reagents. ...................................................... 69 Figure 4. 2: Analytical data of SRFA. .............................................................................. 74 Figure 4. 3: HPLC chromatograms of post-reaction samples of oxidized reageants. ....... 76 Figure 4. 4: UVvis
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