ABSTRACT MORT, SANDRA AMISS. Mass Spectrometric Methods for the Determination of PCB Congeners for Environmental Risk Assessment. (Under the direction of Dr. W. Gregory Cope and Dr. Damian Shea). Our research provides important advances in the evaluation of alternative, cost effective analytical systems for polychlorinated biphenyl (PCB) risk assessment of environmental matrices. This type of evaluation has previously been limited by a reluctance on the part of regulators, site owners and investigators, to specify U.S. EPA Method 1668, the 209-PCB congener analysis recommended for environmental media, including biota, water, sediments and soils. U.S. EPA Method 1668 specifies a high-resolution gas chromatography / high- resolution mass spectrometry detection system (HRGC/HRMS) that is of limited availability in both federal and state environmental regulatory agency laboratories, as well as in contract environmental laboratories. This leads to a high cost for 209-PCB congener analysis and a reluctance to require it for environmental risk assessment. While additional validation is needed, this research indicates that low resolution tandem mass spectrometry (LRMSMS) gas chromatography systems provide adequate PCB congener resolution and detection sensitivity to provide robust data for environmental risk assessment of weathered (i.e., degraded) PCB contamination. Our results provide additional support for the need for 209-PCB congener- specific analyses to thoroughly assess the environmental risks associated with abiotic weathered PCB sources, or to define food web component specific PCB burdens and predator, and ultimately, human risks. Based on observations of waterbody, species and trophic guild specific PCB congener profiles in fish collected from four waterbodies of the Yadkin-Pee Dee River system of North Carolina, alternative human health risk assessment methods suggest that some North Carolina sub-populations ingesting fish from the four Yadkin-Pee Dee waterbodies may not be adequately protected from the potential for increased cancer risks by the N.C. Department of Health and Human Services 2007 fish consumption advisory protocol. Updated population-specific exposure parameters and a more protective threshold cancer risk level indicate elevated risks for frequent consumers of fish from the four waterbodies. Moreover, we evaluated the suitability of the 2015 updated default U.S. EPA trophic magnification factors (TMFs) to estimate the trophic level concentrations of PCBs. Site- specific fish tissue data and the bioavailable fraction of water column PCB congeners collected with passive sampling devices (PSDs) were used in this analysis. The EPA default TMFs over-predicted the level of biomagnification indicated by the site-specific data, which supported the influence of site-specific ecosystem characteristics upon the default parameters to estimate PCB concentrations at various trophic levels. These findings also demonstrated the viability of using low-density polyethylene (LDPE) passive sampling devices (PSDs) to effectively concentrate the bioavailable PCB congener fraction, indicating a time weighted average concentration that would have not been detected by more traditional static sampling methods. The PSD data also pointed to sources other than bioconcentration from the water column as a significant source of exposure of the fish to PCBs. This finding, along with comparison of congener and homolog profiles of the fish and of native Aroclor mixtures, indicated that unique PCB sources likely exist in the four waterbodies and that historical PCB sources known for Badin Lake, may still be contributing to PCB profiles observed in the Badin Lake fish. © Copyright 2017 by Sandra Amiss Mort All Rights reserved Mass Spectrometric Methods for the Determination of PCB Congeners for Environmental Risk Assessment by Sandra Amiss Mort A dissertation submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Zoology Raleigh, North Carolina 2017 APPROVED BY: _____________________________ ______________________________ Dr. W. Gregory Cope Dr. Damian Shea Committee Co-Chair Committee Co-Chair _____________________________ _____________________________ Dr. Ryan J. Heise Dr. Christopher Hofelt _____________________________ Dr. Thomas J. Kwak ii DEDICATION This dissertation is dedicated to my husband, Greg Mort, without whose support and encouragement I could not have completed this effort. iii BIOGRAPHY Sandra Leigh Amiss (“Sandy”) was born on the family farm in Wabash County, IN, where she graduated from Manchester High School, North Manchester, IN. The oldest of three sisters, she grew up with a love of the outdoors and all things science. This lead to completing B.S. degrees in Biology-Chemistry and Biology at Manchester College, North Manchester, IN. While attending Manchester College, she married Greg Mort, also a student at Manchester College, and whom she met while both were attending Manchester High School. After a year as a Research Scientist in a cancer research program at Indianan-Purdue University-Fort Wayne (IPFW), she accepted a laboratory position with an environmental consulting company that sparked her interest in environmental science, where she rose to Vice President of Laboratory and Biological Services. During this time, she developed a focused interest in environmental toxicology, risk assessment, and bioremediation. This lead to the pursuit of a M.S. degree in Biology with emphasis in environmental biology and toxicology at Purdue University - IPFW, while continuing her consulting career. After completion of her M.S., she accepted a position with a bioremediation specialty consulting firm in Raleigh, NC, as the Laboratory Manager and Senior Project Scientist. A few years later, an opportunity arose to work in the Aquatic Toxicology Unit (ATU) with the North Carolina Department of Environment and Natural Resources (NC DENR), in Raleigh, NC. She jumped at the chance to take a position with the ATU, which was a national leader in the development and refinement of the U.S. EPA’s whole effluent toxicology program. While with the ATU, she was awarded the Division of Water Quality Employee of the Year following her development of a suite of toxicity assays to enhance the assessment of aquatic iv ecosystem health. A desire to return to the human-health arena lead to accepting a position with the NC Department of Health and Human Services (DHHS) Division of Public Health (DPH), Raleigh, NC, as the Principal Investigator for an ATSDR/CDC sponsored grant to perform human health risk assessment on federal Superfund sites. At DHHS, she was involved in many high-profile human health issues and was instrumental in enhancing the science of environmental risk assessment and its application to public health issues. It was while at DHHS, she decided to pursue her Ph.D. in Zoology with a minor in Environmental Toxicology at North Carolina State University, while continuing her career at DHHS. During her Ph.D. studies a position as an environmental risk assessor presented itself with the NC DENR Division of Waste Management (DWM). In her current position with the DWM, she works as both a human health and ecological risk assessor, assisting in decisions that directly affect the health of the environment and citizens of North Carolina. v ACKNOWLEDGEMENTS I especially want to thank my committee co-chairs, Dr. Greg Cope and Dr. Damian Shea, as well as my committee members Dr. Chris Hofelt, Dr. Tom Kwak and Dr. Ryan Heise. I appreciate their willingness to take on a non-traditional student, working full-time and pursuing a Ph.D. on a part-time basis. I want to thank all my fellow graduate students and research technicians at NCSU that assisted with this work: Peter Lazaro, Sean Buczek, Laura Belica and Bobby Cope. I want to thank the various agencies that provided financial support and assistance for this research, including the N.C. Department of Health and Human Services Division of Public Health (DHHS DPH), the N.C. Department of Environmental Quality (previously the Department of Environment and Natural Resources) Division of Waste Management and Division of Water Resources (previously the Division of Water Quality), the Stanly County (NC) Health Department, Region 4 of the U.S. Environmental Protection Agency (EPA), the National Institute of Environmental Health Sciences (NIEHS) and the University of North Carolina-Chapel Hill (UNC-CH) Superfund Research Program (SRP), and the North Carolina Wildlife Resource Commission. I also want to especially thank my co-workers and supervisors at DPH and DWM that have accommodated my schedule that has enabled me to pursue my degree. Most of all, I want to acknowledge my husband who has put up with my schedule and my stress, to allow me to pursue my desire to complete a Ph.D., and his constant reminder that “if it was easy, everyone would do it”. vi TABLE OF CONTENTS LIST OF TABLES .................................................................................................................. vii LIST OF FIGURES .................................................................................................................. x CHAPTER 1: Introduction ...................................................................................................... 1 INTRODUCTION ................................................................................................................. 2 REFERENCES ...................................................................................................................