ABSTRACT ZANE, CODY PATRICK. Hazard Assessment of Fluorochemicals Present on Firefighter Gear. (Under the direction of Dr. Bryan Ormond). Per- and polyfluorinated chemicals (PFCs) are a class,4,000 strong, of emerging chemicals of concern. They have permeated much of the environment, from drinking water supplies to household dusts. Much of this has come from their widespread use as a water-, oil-, and dirt-repellent finishes, non-stick coatings for cookware, industrial effluent, and firefighting foams. Most countries have a significant portion of their population with PFCs measured in their blood serum, and studies indicate a plethora of health effects associated with exposure to these chemicals. That being said, certain occupations may face an increased risk of exposure to PFCs, firefighting being one of them. Firefighters come into contact with a wide array of chemicals due to their occupation: phenols, phthalates, polycyclic aromatic hydrocarbons, heavy metals, carbon monoxide, etc. However, most of those chemicals are due to situations they encounter on the job. A few years ago, the firefighting community started to become weary of the personal protective equipment, known as turnout gear, they wear while facing those situations. They were misinformed when they were told that their gear was made from PFCs. Yet, it was still unknown whether they had increased exposure to PFCs from latent chemicals on their gear. The following dissertation aimed to develop a risk assessment for the firefighting community for their exposure to PFCs. This was completed via a three-branch approach: an in- depth literature review to determine health effects and current exposure levels for firefighters, quantification of two PFCs in unused gear from a 20-year range, and a durability assessment of the PFCs present on the gear. Ultimately, it was determined that firefighters have minimal risk of exposure to PFCs from their gear. Quantification of the 20-year range of turnout gear determined the highest level of perfluorooctanoic acid (PFOA) to be at 14.83 ng/cm2. With dermal exposure being the most likely pathway to exposure from PFCs on gear, this concentration is 1,000 times lower than the lowest concentration tested for dermal studies of PFCs. The study found no detectable limits of perfluorooctane sulfonate (PFOS). The durability studies determined that the PFCs, present in the form of durable water repellent (DWR) finishes, were durable up to 120-hours of UV exposure and 50 standard NFPA 1851 wash cycles, separately. Outer shell material was exposed to UV up to 120 hours. No drop in ISO 6530 water repellency or goniometer contact angle was indicated. Outer shell material was also exposed up to 100 standard NFPA 1851 wash cycles. Results from ISO 6530 testing indicated a decrease in water repellency after 50 washes, but no more than a 20% loss of water repellency. Additionally, this dissertation developed and validated an extraction procedure for PFCs from textile materials. The study indicates that a wide array of extraction techniques are viable but based on sample size, time, and solvent volume the sonication and pressurized solvent extractor methods, without evaporation, were determined to be the most beneficial. While the following dissertation was thorough and answered many questions the firefighting community had about their gear there are still things to consider. Much of the published research indicates elevated levels of sulfonated PFCs in firefighters blood. This may be due to use of aqueous film forming foams but further investigation is needed. Although, that does not mean that they do not have higher exposure rates © Copyright 2020 by Cody Patrick Zane All Rights Reserved Hazard Assessment of Fluorochemicals Present on Firefighter Gear by Cody Patrick Zane 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 Fiber and Polymer Science Raleigh, North Carolina 2020 APPROVED BY: _______________________________ _______________________________ Dr. Bryan Ormond Dr. Melissa Pasquinelli Committee Chair _______________________________ ______________________________ Dr. Emily Griffith Dr. Ronald Baynes DEDICATION I dedicate the following dissertation to my grandmother, Grace Cecelia Zane, better known to me as Grammie. Gram, I may not have had long with you in this life but you taught me so many important life lessons that I will never forget. Unfortunately, it took me a few years after you passed to finally realize what you were teaching me. Regardless, I know that every ounce of what you taught me went into getting this degree. I could not have done this degree without those lessons. They kept reminding me to find and surround myself with those I love and work with them, to help us all achieve our own goals. Most importantly, you taught me pure, unadulterated compassion. Love and care for everyone, regardless of what they have done to you because hatred will only eat you up. I love you so much, miss you everyday, and thank you for everything you have done, and will do, for me. ii BIOGRAPHY Cody Patrick Zane is an internationally unrecognized scientist, baker, chef, student leader and scholar, who specializes in bread, smoked meats, mental health activism, analytical chemistry and personal protective equipment (PPE). Born in the wee hours of a Tuesday morning, after his mother decided to do The Twist while being nine-months pregnant, Cody turned out to be a tiny terror to his parents and the reason for many of their grey hairs. Despite all the mayhem he caused in his young life, Cody found his way as he stumbled from one passion to the next. In 2011, Cody started his baccalaureate degree in Polymer and Color Chemistry in the College of Textiles at North Carolina State University where he graduated Magna Cum Laude in 2015. Unsure of what to do next, Cody entered graduate school, at his alma mater, for a Masters of Science in Textile Chemistry, under the advisement of Dr. Melissa Pasquinelli and Dr. Nelson Vinueza, which he graduated Suma Cum Laude in 2017. It was at this juncture where Cody started understanding how all of his passions aligned. He enjoyed teaching, mentoring, and research/projects that had direct impacts on communities. As someone who could not sit still, he decided he would go on to complete a Ph.D. in Fiber and Polymer Science (yet again at North Carolina State University) under the advisement of Dr. Bryan Ormond in the Textile Protection and Comfort Center, as well as being a Mental Health Ambassador with the Counseling Center on campus. Simultaneously, Cody lead a charge for his University community to Stop the Stigma surrounding mental health for graduate students and to discover, and understand, the occupational exposure risk of firefighters to per- and polyfluoroalkyl substances. At the completion of his degree, Cody has a desire to go into industry to continue working on PPE for first responders and military personnel. iii ACKNOWLEDGMENTS This page is not enough for me to acknowledge every person I think has helped me get to the competition of this degree. If you know me and I have not mentioned you here, please understand that you have done something to help me on my path and I appreciate you wholeheartedly. While there are so many people I could acknowledge there are a handful I would like to mention. First and foremost, Bryan Ormond, my advisor and friend. You have supported me through every single thing that I have put my mind to and I definitely would not be the research and activist I am today without having you as my academic father…maybe academic brother. Next I would like to acknowledge my crazy, dopey, loving family. Sometimes, as the youngest, I feel as if there is no where for me to go that hasn’t already been achieved by everyone else in this family. But every day you dispel that belief, remind me how strong I am, what good I am doing, and give me unconditional love. I love you so much. My Bella…we may not have been together for my entire time in grad school but you have supported me through the hardest times. You are my pillar and I don’t know where I would be today without you. You remind me everyday to love the day and take charge of it. I love you so much that a Unidentified Ferby Object could not break it. Lastly, I have to acknowledge Miss Zeta Omega Zane (Lovebug) and Mr. Chi Rho Zane (BeauxBeaux). They may never be able to read this, but that doesn’t mean I am not going to thank them for the load of unconditional love they wash me with everyday. Your Cody could not have asked for two better puppies to help him through this experience. You always knew when I needed love and support and would cuddle me to help me feel better. You will always have a place in my heart, I love you. iv TABLE OF CONTENTS LIST OF TABLES ....................................................................................................................... ix LIST OF FIGURES ..................................................................................................................... xi CHAPTER 1: Purpose of Research and Research Objectives .........................................................1 1.1. Purpose of Research ......................................................................................................... 1 1.2. Research Objectives ......................................................................................................... 2 1.2.1. Understanding of PFC Concentration