SUNY College of Environmental Science and Forestry Digital Commons @ ESF Dissertations and Theses Fall 12-2019 Freshwater Paralytic Shellfish oisoningP Toxins and other Cyanobacterial Neurotoxins in New York Lakes Zacharias J. Smith SUNY College of Environmental Science and Forestry Follow this and additional works at: https://digitalcommons.esf.edu/etds Part of the Algae Commons, Bacteria Commons, Environmental Microbiology and Microbial Ecology Commons, and the Toxicology Commons Recommended Citation Smith, Zacharias J., "Freshwater Paralytic Shellfish Poisoning Toxins and other Cyanobacterial Neurotoxins in New York Lakes" (2019). Dissertations and Theses. 122. https://digitalcommons.esf.edu/etds/122 This Open Access Dissertation is brought to you for free and open access by Digital Commons @ ESF. It has been accepted for inclusion in Dissertations and Theses by an authorized administrator of Digital Commons @ ESF. For more information, please contact [email protected], [email protected]. Freshwater Paralytic Shellfish Poisoning Toxins and other Cyanobacterial Neurotoxins in New York Lakes by Zacharias J. Smith A dissertation submitted in partial fulfillment of the requirements for the Doctor of Philosophy Degree State University of New York College of Environmental Science and Forestry Syracuse, New York December 2019 Department of Chemistry Approved by: Gregory Boyer, Major Professor Roxanne Razavi, Chair, Examining Committee Avik Chatterjee, Department Chair S. Scott Shannon, Dean, The Graduate School i © Copyright Zacharias J. Smith All rights reserved ii Acknowledgments I gratefully acknowledge the support of Dr. Gregory Boyer throughout the completion of my degree, where without his technical and academic support this achievement would not have been possible. I would also like to acknowledge my steering committee members, Dr. Dave Kieber and Dr. John Hassett for their guidance throughout the process. I would like to extend further thanks to Dr. Kimberly Schulz for her assistance with statistical analyses and for her time attending as an additional steering committee member and as an examiner. Thank you as well to Dr. Gord Paterson for his guidance and for acting as a member of my examination committee. I would like to thank my lab mates for their help and friendship over the years. Exceptional thanks goes out to Bofan Wei for his help sampling at Butterfield Lake and for helping bring that project to completion. Additionally, I would like thank Bofan for his friendship and loyalty over the years, especially through challenging times. I would further like to thank Kristen Slodysko, a stranger from Seattle who somehow knew a friend-of-a-friend and who ended up on the other side of the United State in the same laboratory but who also became an amazing friend! I want to thank Kristen for all of the times we got coffee together and had a good time hanging out. Additionally, Kristen was responsible for bringing out my interest and knowledge of statistics, which turned out to be critical. Although our discussions about statistics were complex and sometimes frustrating, great thanks goes out to her for taking the time to help me get started in this area. I would like to thank Adam Marshall for his time with me early on in the process of earning my doctorate. Not only was and is Adam a great friend, but he helped me push through the several highly stressful first-years of my doctorate. His friendship is greatly treasured. Finally, I would like to thank my parents, Jonathan Smith and Sara Jessie Tarr. Without their loving support and compassion, I would never have made it to graduate school, let alone complete a doctorate. I could not have asked for any more from them. They have offered me support, love, guidance, care, tenderness, appreciation, and a constant source of companionship and conversation. They have made me a better person, a better scientist, and I could never dream of having more. iii Table of Contents List of Tables ........................................................................................................................................................... xv List of Figures ........................................................................................................................................................ xvii List of Supplementary Information ..................................................................................................................... xx Abstract ............................................................................................................................................................... xxviii List of Abbreviations and Symbols .................................................................................................................. xxvi Introduction ................................................................................................................................................................ 1 The Nature of the Problem .................................................................................................................................... 1 1.1 Harmful Cyanobacteria and Neurotoxins ................................................................................................. 1 1.2 Hypothesis and Objectives .......................................................................................................................... 4 1.3. References ..................................................................................................................................................... 5 Background and Context ........................................................................................................................................ 11 2.1 Eutrophication, Climate Change, and the Expansion of Harmful Algal Blooms .................................. 11 2.1.1 Global Distribution of Harmful Algae and some Factors Related to their Proliferation ............... 11 2.1.2 Public Perception and Economic Impact of HABs .............................................................................. 12 2.2 Cyanobacterial Toxin Review ....................................................................................................................... 14 2.2.1 Microcystins .............................................................................................................................................. 14 2.2.1.1 Background ........................................................................................................................................ 14 2.2.2.2 Methods for Detection ...................................................................................................................... 15 2.2.2.3 Toxicity and Health Effects from Exposure to Microcystins....................................................... 16 2.2.2 Cylindrospermopsin................................................................................................................................ 19 2.2.2.1 Background ........................................................................................................................................ 19 2.2.2.2 Methods for Detection ...................................................................................................................... 19 2.2.2.3 Toxicity and Health Effects from Exposure to Cylindrospermopsin ........................................ 20 2.2.3 Anatoxin-a, homo-anatoxin, and dihydro-anatoxin ........................................................................... 21 2.2.3.1 Background ........................................................................................................................................ 21 2.2.3.2 Methods for Detection ...................................................................................................................... 22 2.2.3.3 Risks from Exposure to Anatoxin-a and Derivatives ................................................................... 23 2.2.3.4 Anatoxin Regulatory Guidelines .................................................................................................... 25 2.2.4 Anatoxin-a(s) ............................................................................................................................................ 26 2.2.5 Paralytic Shellfish Poisoning Toxins ..................................................................................................... 28 2.2.5.1 Background ........................................................................................................................................ 28 2.2.5.2 Methods for Detection ...................................................................................................................... 30 2.2.5.2.1 Receptor Binding Assay ................................................................................................................ 31 2.2.5.2.2 Saxitoxin and Neosaxitoxin Enzyme Linked Immunosorbent Assay (ELISA) ..................... 31 iv 2.2.5.2.3 Oxidation and Fluorescence Detection with High Performance Liquid Chromatography . 33 2.2.5.2.4 Mass Spectrometry ........................................................................................................................ 35 2.3.5.3 Risks from Exposure to Paralytic Shellfish Poisoning Toxins .................................................... 41 2.3.5.4 Paralytic Shellfish Poisoning Toxin Regulatory Guidelines ....................................................... 41 2.4 Historical Evaluation