Development and Application of Passive Samplers for Assessing Air and Freely Dissolved Concentrations of Hydrophobic Organic Contaminants by Adesewa A. Odetayo, B.Tech., M.Sc. A Dissertation In Civil, Environmental and Construction Engineering Submitted to the Graduate Faculty of Texas Tech University in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Approved Dr. Danny D. Reible Chair of Committee Dr. Chongzong Na Dr. Weile Yan Dr. Mark Sheridan Dean of the Graduate School December 2020 Copyright 2020, Adesewa Odetayo Texas Tech University, Adesewa Odetayo, December 2020 Acknowledgements This research was supported by funding from U.S Army Corps of Engineer (USACE) and U.S Army Engineer Research Development Center (ERDC) (contract # W912HZ-17-2-0019), and the Environmental Security Technology Certificate Program (ESTCP) (contract # ER 201735). Special thanks to the crew from ERDC for their support during all the field sampling trips. Firstly, my sincere appreciation goes to my supervisor, Dr. Danny Reible for his help, guidance, and tremendous support throughout the course of my doctoral study, without whom I would have accomplished this milestone. I would like to also extend my gratitude to my committee members for their time and constructive inputs to my research. My Doctoral research experience was made possible because of so many individuals starting with Magdalena Rakowska, who is always available to help and provide intellectual insights pertaining my research. My adopted brother, Uriel de Jesús Garza Rubalcava who cheered me up and always available to help. Tariq Hussain and Alex Smith who I would most likely meet in the Lab at nights or weekends working on their individual research and fellow passive sampling buddy. My office pals, Hasti Ziaei and Ilektra Drygiannaki, who provided multiple layers of fun to my Ph.D. experience. A special thank you to Brad Thornhills and the Reible research group for your various support during my Ph.D. journey. To my amazing husband, Oluwaseyi who shared this journey with me, always ready to help with proofreading and put up with me or the absence of me. I sincerely appreciate your love, moral support, patience, and sacrifice for the past five years. I would like to also thank my parents, siblings, family-in-love and friends for their supports, prayers, and words ii Texas Tech University, Adesewa Odetayo, December 2020 of encouragement. You are all shades of amazing, I couldn’t have achieved this without you. Last and most importantly, my deepest gratitude goes to the maker of my life, the orchestrator of all things, the foundation of the world, my lord and savior, Jesus Christ. Thank you, Lord, for the assurance I have in your words, you are the lamp unto my feet and the light unto my path. iii Texas Tech University, Adesewa Odetayo, December 2020 Table of Contents Acknowledgements ............................................................................................................. ii Abstract ........................................................................................................................... ix List of Tables .................................................................................................................... xii List of Figures .................................................................................................................. xiii Chapter 1 Introduction ........................................................................................................ 1 1.1. Background and Motivation ............................................................................ 1 1.2. Research Objectives ........................................................................................ 3 1.3. Dissertation Outline......................................................................................... 4 References ............................................................................................................... 5 Chapter 2 Literature Review ............................................................................................... 8 2.1. Hydrophobic Organic Contaminants (HOCs) ................................................. 8 2.1.1. Polychlorinated biphenyls (PCBs) ................................................. 8 2.1.2. Polycyclic aromatic hydrocarbons (PAHs) .................................... 9 2.2. Health implications of HOCs uptake ............................................................ 10 2.3. Environmental Risk Prediction, Assessment, and Indication ....................... 15 2.3.1. Freely dissolved concentrations in sediment or aquatic systems ......................................................................................... 16 2.3.2. Airborne concentrations ............................................................... 17 2.4. Passive sampling methods ............................................................................. 17 2.4.1. Emergence of passive sampling methods .................................... 17 2.4.2. Choice of passive samplers’ sorbents .......................................... 18 2.4.2.1. Semipermeable membrane devices ........................................ 18 2.4.2.2. XAD-2 resins ......................................................................... 19 2.4.2.3. Polyurethane foams ................................................................ 20 2.4.2.4. Polyethylene ........................................................................... 21 2.4.2.5. Polydimethylsiloxane ............................................................ 22 2.4.2.6. Polyoxymethylene ................................................................. 23 2.5 Theory of passive sampling ............................................................................ 24 2.5.1. Time series exposure ................................................................... 25 2.5.2. Multiple polymer thicknesses ...................................................... 25 2.5.3. Performance Reference Compounds (PRCs) ............................... 26 2.6. Summary ....................................................................................................... 27 References ............................................................................................................. 29 iv Texas Tech University, Adesewa Odetayo, December 2020 Chapter 3 Research Methodologies .................................................................................. 36 3.1. Overview of the Study Area .......................................................................... 36 3.2. Reagents and Materials ................................................................................. 39 3.3. Analytical Instrument.................................................................................... 40 3.3.1. High Performance Liquid Chromatography (HPLC) .................. 40 3.3.2. Gas Chromatography– Mass Spectrometer (GC-MS) ................. 40 3.3.3. Gas Chromatography– Triple quad Mass Spectrometer (GC-TQMS) ................................................................................. 41 3.4. Sediment characterization ............................................................................. 41 3.5. Water sampling ............................................................................................. 42 3.6. Porewater sampling ....................................................................................... 42 3.7. Air sampling .................................................................................................. 42 3.8. Quality Assurance and Quality Control (QAQC) ......................................... 43 Chapter 4 Development of polyoxymethylene passive sampler for assessing air concentrations of PCBs at a confined disposal facility (CDF) ........................ 44 Abstract .............................................................................................................. 45 4.1. Introduction ................................................................................................... 46 4.2. Materials and Methods .................................................................................. 48 4.2.1. Reagent, Material and Instrument ................................................ 48 4.2.2. Sediment and Water PCB measurements .................................... 49 4.2.3. Polymeric samplers ..................................................................... 49 4.2.4. Laboratory Experiments .............................................................. 49 4.2.5. Preliminary deployment of POM Air samplers (PAS) at the CDF site ....................................................................................... 50 4.2.6. Meteorological data at the CDF .................................................. 52 4.2.7. Instrument analysis and Quality control ...................................... 53 4.3. Results and discussion ................................................................................... 54 4.3.1. Dissolved PCB concentrations in laboratory slurries .................. 54 4.3.2. Uptake kinetics and equilibrium on POM sampler ..................... 57 4.3.3. Air concentration of PCB congeners at the CDF ........................ 60 4.3.4. Comparison between PAS and HVAS of PCB congeners 15, 18, 20/28 and 31………………. ........................................... 61 4.4. Conclusions ................................................................................................... 63 Acknowledgements ..............................................................................................