Thermodynamic Activity and Fugacity Applied to Risk Assessment and Criteria Development of Petroleum Hydrocarbons by Meara Crawford B.Sc. (Hons., Biology & Earth and Ocean Science), University of Victoria, 2007 Research Project Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Resource Management Report No. 604 in the School of Resource and Environmental Management Faculty of Environment © Meara Crawford 2014 SIMON FRASER UNIVERSITY Fall 2014 Approval Name: Meara Crawford Degree: Master of Resource Management Title: Thermodynamic Activity and Fugacity Applied to Risk Assessment and Criteria Development of Petroleum Hydrocarbons Report No.: 604 Examining Committee: Chair: Mandy McDougall Master of Resource Management Candidate Dr. Frank Gobas Senior Supervisor Professor Mr. Don MacDonald Supervisor Principal MacDonald Environmental Sciences Ltd. Mr. Peter Kickham Supervisor Risk Assessment Officer British Columbia Ministry of Environment Date Defended/Approved: November 26, 2014 ii Partial Copyright Licence iii Abstract Thermodynamic activity and fugacity were used to describe the toxic effects concentrations of petroleum hydrocarbons (PHCs) across a range of PHCs and PHC mixtures in different media (water, sediment, soil, lipid), for a variety of effects (e.g., survival, growth) on a variety of species. There is a similar range in activity associated with PHC toxicity across chemicals, media, species, and effects, and PHC mixtures of varying composition. Therefore, the lower 5th percentile of all PHC toxicity data (activity = 0.003), or corresponding lipid-normalized concentration (4.36 mol/m3) or volume fraction (0.0008 m3/m3) calculated from activity at equilibrium can be applied to integrate a broad range of effects data into risk assessments and criteria development. When expressed as activity, the current PHC mixture criteria for sediment, soil, and water that are applicable in British Columbia overlap or exceed the range of activities associated with toxic effects, and therefore, these criteria may be underestimating environmental risks from PHC exposure. Keywords: petroleum hydrocarbons; thermodynamic activity; risk assessment iv Acknowledgements To Dr. Frank Gobas, I feel truly fortunate to have had this opportunity to work and share time with you. Your depth of knowledge, and passion for science, as well your sense of wonder and honest curiosity about the world around you are inspiring. The open and respectful way in which you include those around you is a model I will always look to emulate. Thank you very much for your patience and encouragement throughout this degree, and for reminding me that you don’t have to save the whole world in a day. To Don MacDonald, thank you for all of your support, not only in the time you’ve taken to contribute to this project, but also throughout the years that I have been fortunate to work with you. It was my experiences at MESL that really showed me the field of environmental toxicology as the perfect melding of many of my academic interests, and ultimately, convinced me to pursue this degree. To Peter Kickham, thank you for jumping in and being a part of this project. I really appreciate your honesty and valuable practical perspectives on future applications and context for this research. To Victoria Otton, thank you for all of your technical and emotional support, and really taking the time to listen and encourage me. I can not imagine the last few years without your guidance. I would also like to thank Fugacity Club – I could not have asked for a better group of peers to learn from - the last few years were all the more richer because they were shared with you. Finally, thank you to my brothers for forging the way, to my parents for believing in my power always, and to Silas for unwaveringly riding the roller coaster with me. v Table of Contents Approval ............................................................................................................................. ii Partial Copyright Licence .................................................................................................. iii Abstract ............................................................................................................................. iv Acknowledgements ............................................................................................................ v Table of Contents .............................................................................................................. vi List of Tables ..................................................................................................................... ix List of Figures ................................................................................................................... xi List of Acronyms ............................................................................................................. xiv Glossary ........................................................................................................................... xv 1. Introduction .............................................................................................................. 1 1.1. Petroleum Resource Industry in British Columbia ................................................... 1 1.2. Petroleum Hydrocarbons ......................................................................................... 2 1.3. Environmental Management of Petroleum Hydrocarbons ....................................... 3 1.4. Wildlands Ecological Context ................................................................................... 3 1.5. Research Objectives ................................................................................................ 6 2. Background: Chemistry and Toxicology of Petroleum Hydrocarbons .............. 8 2.1. Chemistry and Toxicology of Individual Petroleum Hydrocarbons ........................... 8 2.2. Chemistry and Toxicology of Mixtures of Petroleum Hydrocarbons ...................... 10 2.3. Brief History of Activity & Fugacity Applications ..................................................... 12 3. Methods .................................................................................................................. 14 3.1. General Methodology ............................................................................................. 14 3.2. Activity & Fugacity .................................................................................................. 14 3.2.1. Thermodynamic Description of Activity & Fugacity ................................... 14 3.2.2. Lipid-phase Concentration and Volume Fraction ...................................... 19 3.2.3. PHC Mixture Calculations ......................................................................... 21 3.2.4. Details of Activity, Fugacity, CL, and VC/VL Calculations ........................... 22 Chemical Property Data of PHCs .......................................................................... 28 Chemical Properties of PHC Mixture Components ......................................... 29 3.3. Toxicological Effects Data for Individual and Mixtures of Petroleum Hydrocarbons Expressed as Activity, Fugacity, and Lipid-phase Concentration and Volume Fraction ...................................................................... 32 3.3.1. Compilation of Toxicological Effects Data for Individual PHCs ................. 32 3.3.2. Compilation of Toxicological Effects Data for PHC Mixtures .................... 37 Water-based PHC Mixture Toxicity Data .............................................................. 38 Soil-based PHC Mixture Toxicity Data .................................................................. 39 Sediment-based PHC Mixture Toxicity Data ......................................................... 39 Lipid-based PHC Mixture Toxicity Data ................................................................ 40 3.3.3. Categorization of Toxicological Effects Data ............................................. 40 3.3.4. Activities and Fugacities Describing the Toxicity of Individual PHCs ........ 41 Across-Chemical Comparison of Individual PHC Toxicity ..................................... 41 Across-Media Comparison of Individual PHC Toxicity .......................................... 42 vi Internal and External Media ............................................................................ 42 Water, Porewater, Sediment, and Lipid Media ............................................... 42 Across-Species Comparison of Individual PHC Toxicity ....................................... 42 Species Categories ......................................................................................... 42 Individual Species ........................................................................................... 43 Across-Effects and Across-Endpoints Comparison of Individual PHC Toxicity ............................................................................................................ 43 3.3.5. Activities and Fugacities Describing the Toxicity of PHC Mixtures ........... 43 3.4. Toxicity of Petroleum Hydrocarbon Mixtures Compared to Toxicity of Individual Petroleum Hydrocarbons ....................................................................... 43 3.5. Comparison of Activity- and Fugacity-based Approach with Current Approaches to PHC Risk Assessment and Guideline Development ..................... 44 3.5.1. Current PHC Mixture Guidelines ..............................................................