AN ABSTRACT OF THE DISSERTATION OF Carey E. Donald for the degree of Doctor of Philosophy in Toxicology presented on April 17, 2017 Title: Advances in Passive Sampling: Measuring Chemical Transport and Human Exposures Abstract approved: Kim A. Anderson Passive sampling devices have been used for decades to measure complex mixtures of bioavailable organic chemicals in a variety of environmental media. More recently passive sampler applications have expanded beyond monitoring chemical concentrations, and this dissertation continues to advance methods of passive sampling on many fronts. Despite their growing use, no practical, evidence-based guidelines exist to ensure concentrations of chemicals sequestered in passive samplers are stable in transport and storage. We demonstrated that concentrations of semivolatile chemicals sequestered within passive samplers would be stable with low-cost shipping from isolated locales by simulating in the laboratory a worst-case scenario at 35 °C for two weeks. Quantitative measures of the flux of semivolatile chemicals between soil and air have been limited by the challenges of collecting soil and estimating chemical fugacity from soil. We avoided these pitfalls by adapting passive sampling equipment to directly sample gas-phase chemicals in air above the soil. The sensitivity of the novel technique was demonstrated at three disparate sites, where volatilization was measured at a site with historically contaminated soil, and deposition was measured at another site with a recent oil spill and fire. In a related study, we deployed the same equipment on artificial turf fields to provide the first quantitative measure of semivolatile flux between artificial turf and overlying air. We detected an additional 26 compounds that have not been previously associated with artificial turf, including some that have known human health impacts. Finally, passive sampling principles were applied to measure chemicals in the human personal environment, using a newly-developed silicone passive sampler wristband. Nineteen pesticides were detected that were not reportedly used among 35 rural farmer participants, demonstrating the utility of the wristband in measuring personal exposures to pesticides. Pesticide concentrations in multiple wristbands, worn by a participant over time, were more similar to each other than to other participants, signifying the uniqueness of personal environments and the importance of taking personalized measurements when assessing risk. The advancements in this dissertation capitalize on the features of passive sampling techniques: easy, yet robust, transport capabilities were demonstrated to provide evidence-based transport criteria; ability to directly measure gas-phase chemicals led to quantitative flux measurements from soil and artificial turf; non-selective organic chemical sequestration allowed for identification of unexpected, or previously unreported chemicals; and the polymer qualities that mimic biological membranes sampled the bioavailable fraction for comparing human exposures. The advancements herein provide logistical solutions and sensitive measures of chemical transport and human exposures, and contribute to the expanding range of possibilities for passive sampling. ©Copyright by Carey E. Donald April 17, 2017 All Rights Reserved Advances in Passive Sampling: Measuring Chemical Transport and Human Exposures by Carey E. Donald A DISSERTATION submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Presented April 17 2017 Commencement June 2017 Doctor of Philosophy dissertation of Carey E. Donald presented on April 17, 2017. 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 authorizes release of my dissertation to any reader upon request. Carey E. Donald, Author ACKNOWLEDGEMENTS I greatly appreciate the numerous mentors throughout my education. To my advisor, Dr. Kim Anderson, thank you for dedicating time to me, and for letting me be a part of your team. Thank you to the faculty and staff of Department of Environmental and Molecular Toxicology for the chance to be a student and the countless opportunities and support provided to me in the past years. Thank you to my committee, Dr. Robert Tanguay, Dr. Staci Simonich, Dr. Jennifer Field, and Dr. Molly Kile, for guidance. To my undergraduate advisor, Dr. Rob Bachman, thank you for sparking my interest in chemistry by pointing it out in everyday life. Thank you, Glenn Wilson and Ricky Scott, for teaching me volumes about analytical chemistry, and being a reliable source for all my troubleshooting guidance. Thank you, Gary Points, for all the help you’ve provided. Kevin Hobbie and Josh Willmarth, thanks for the laughs and all the ways you made me more efficient. Dr. Alan Bergmann, Holly Dixon, Pete Hoffman, Jamie Minick, and Dr. Steven O’Connell, thanks for the easy, candid conversations about concepts that I couldn’t understand until I thought out loud. Dr. Blair Paulik, thank you for pulling double-duty as an excellent friend and academic peer—I’m glad we hit it off so early. Thanks, Dr. Pat Haben, I can’t imagine life in Corvallis without you. Thank you to my wonderful friend, Caitlin Neal Gold—she and her family and friends are the reason I came to know Oregon as my second home. Alan, thank you thank you for all your support, big and small. I can’t wait for the next adventure either. Finally, I thank my family for supporting me all along. I’m grateful for you, and I’m delighted that our family is growing. Mom and Dad, you never once gave me the impression that I couldn’t accomplish something great, though I am sorry that I chose to do it 2,097 miles away from you. CONTRIBUTION OF AUTHORS In Chapter 2, Marc R. Elie provided experimental design, and performed instrumental analysis. Brian W. Smith performed and advised in statistical analysis. Peter D. Hoffman acquired UV transmittance data. Kim A. Anderson assisted in experimental design and manuscript preparation. In Chapter 3, Kim A. Anderson assisted in experimental design and manuscript preparation. In Chapter 4, Kim A. Anderson assisted in experimental design and manuscript preparation. In Chapter 5, Richard P. Scott performed GC-ECD method enhancement. Kathy L. Blaustein and Mary L. Halbleib coordinated the study in Senegal and Institutional Review Board approval, and communicated with volunteer. Makhfousse Sarr participated in study design and coordinated support staff and volunteer participants. Paul C. Jepson participated in study design, coordinated the study in Senegal, and communicated results to volunteer participants. Kim A. Anderson participated in study design and manuscript preparation. TABLE OF CONTENTS Page Chapter 1 – Introduction .................................................................................................................. 2 Chemical mixtures .............................................................................................................. 2 Passive sampling techniques ............................................................................................... 3 Dissertation outline ............................................................................................................. 3 Chapter 2 – Transport stability of pesticides and PAHs sequestered in polyethylene passive sampling devices .............................................................................................................................. 5 Abstract ............................................................................................................................... 6 Introduction ......................................................................................................................... 6 Materials and Methods ........................................................................................................ 8 Results and Discussion ..................................................................................................... 10 Chapter 3 – Assessing soil-air partitioning of PAHs and PCBs with a new fugacity passive sampler ........................................................................................................................................... 18 Abstract ............................................................................................................................. 19 Introduction ....................................................................................................................... 19 Materials and Methods ...................................................................................................... 21 Results ............................................................................................................................... 25 Discussion ......................................................................................................................... 27 Chapter 4 – Contaminant flux from artificial turf .......................................................................... 42 Abstract ............................................................................................................................. 42 Introduction ......................................................................................................................