FORENSIC PAH ASSESSMENT OF THE SYDNEY TAR PONDS AND THE SURROUNDING ENVIRONMENT USING PAH FINGERPRINT ANALYSIS by Devin MacAskill Submitted in partial fulfilment of the requirements for the degree of Master of Applied Science at Dalhousie University Halifax, Nova Scotia August 2014 © Copyright by Devin MacAskill, 2014 i. I would like to dedicate this thesis to my wife, Natalie MacAskill, whose support and patience gave me the opportunity to pursue and complete this research project. Table of Contents Page # List of Tables ............................................................................................................................................... vi List of Figures ............................................................................................................................................ viii Abstract ...................................................................................................................................................... viii List of Abbreviations Used .......................................................................................................................... ix Acknowledgements ....................................................................................................................................... x Chapter 1 - Introduction ................................................................................................................................ 1 1.1. Hypothesis ...................................................................................................................................... 2 1.2. Multiple Techniques Approach ...................................................................................................... 2 1.3. Project Background ........................................................................................................................ 3 Chapter 2 - Literature Review ....................................................................................................................... 4 2.1. Coke Production ............................................................................................................................. 4 2.2. Polycyclic Aromatic Hydrocarbons (PAHs) .................................................................................. 5 2.3. PAH Risk and Toxicity .................................................................................................................. 8 2.4. PAH Partitioning and Environmental Fate Modelling ................................................................... 8 2.5. Sydney Harbour Sediment Deposition Rates ................................................................................. 9 2.6. PAHs in Coal ............................................................................................................................... 10 2.7. Degradation of PAHs ................................................................................................................... 10 2.8. PAH Analytical Procedures ......................................................................................................... 11 2.8.1. Analysis .................................................................................................................................. 12 2.8.2. Quality Assurance .................................................................................................................. 12 2.8.3. Detection Limits ..................................................................................................................... 12 2.8.4. Determination of PAHs in Soil by GC-MS ............................................................................ 12 2.9. Use of Non-Detect Data ............................................................................................................... 13 2.10. PAH Fingerprint Analysis ............................................................................................................ 14 Chapter 3 - Proposed Methodologies .......................................................................................................... 16 3.1. Tiered Approach ........................................................................................................................... 16 3.2. Use of Non-Detect Data ............................................................................................................... 18 3.3. Data Normalization ...................................................................................................................... 19 3.4. Mass Fractions versus Molar Fractions ........................................................................................ 20 3.5. FALCON ...................................................................................................................................... 24 3.6. Fingerprint Methods ..................................................................................................................... 25 3.6.1. Chromatograms ......................................................................................................................... 25 3.6.2. Histograms ................................................................................................................................ 27 3.6.3. Correlation Analysis ................................................................................................................. 27 3.6.4. Principal Component Analysis ................................................................................................. 28 3.6.5. Diagnostic Ratios ...................................................................................................................... 30 3.6.6. Mann Whitney Non-Parametric Test ........................................................................................ 31 Chapter 4 - Case Study ................................................................................................................................ 33 4.1. The Sydney Tar Ponds and Coke Ovens ...................................................................................... 33 4.2. Solidification / Stabilization ......................................................................................................... 35 4.3. Data Sources ................................................................................................................................. 36 4.4. Standard Reference Material SRM 1597a .................................................................................... 36 4.5. Sample Data ................................................................................................................................. 36 4.5.1. Monitoring Program - Soil and Sediment Sampling ................................................................ 36 4.5.2. Tar Ponds Sediments ................................................................................................................ 37 4.5.3. Upstream Surface Water Sediments ......................................................................................... 38 4.5.4. Harbour Sediment Grabs .......................................................................................................... 38 4.5.5. Sediment Traps ......................................................................................................................... 39 4.5.6. Slo-Corer Harbour Sediments ................................................................................................... 39 4.5.7. Urban Background Soil ............................................................................................................. 40 4.6. Limitations ................................................................................................................................... 40 Chapter 5 - Results and Discussion ............................................................................................................. 41 5.1. Chromatograms ............................................................................................................................ 41 5.2. Histograms ................................................................................................................................... 42 5.3. Correlation Analysis ..................................................................................................................... 48 5.4. Principal Components Analysis ................................................................................................... 53 5.5. Diagnostic Ratios ......................................................................................................................... 59 5.6. Mann Whitney Non-Parametric Test ........................................................................................... 67 Chapter 6 - Conclusions and Recommendations ........................................................................................ 69 6.1. Fingerprint Technique Summaries ............................................................................................... 69 6.1.1. Chromatograms ......................................................................................................................... 69 6.1.2. Histograms ................................................................................................................................ 69 6.1.3. Correlation Analysis ................................................................................................................. 70 6.1.4.