EVALUATING THE EFFECTS OF WASTEWATER TREATMENT ON MARINE SEDIMENT CHEMISTRY IN HALIFAX HARBOUR, NOVA SCOTIA by Gwen A. Williams Submitted in partial fulfillment of the requirements for the degree of Master of Science at Dalhousie University Halifax Nova, Scotia July 2010 © Copyright by Gwen A. 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Effects 11 1.2.1.3.1 Granulometric Methods 12 1.2.1.3.2 Normalization 13 1.2.1.3.3 Regression 14 1.2.2 Organic Contaminants 14 1.2.2.1 Polycyclic Aromatic Hydrocarbons 15 1.2.2.2 Coprostanol 18 1.2.3 Bioavailability 20 1.2.3.1 Acid Volatile Sulphides 22 1.2.4 Sediment Quality Values 23 Chapter 2 Background 25 2.1 Geological History of Halifax Harbour 25 2.1.1 Formation of Halifax Harbour 25 2.1.2 SurficialGeology 28 2.1.3 Harbour Circulation 28 2.1.4 Sediment Input 29 2.2 Human History of Halifax 31 IV 2.2.1 Human History of Bedford 32 2.3 Sources of Contamination 33 2.4 Wastewater Treatment 35 2.4.1 Primary and Advanced Primary Wastewater Treatment 36 2.4.2 Secondary Wastewater Treatment 38 2.4.3 Harbour Solutions Project 39 2.4.4 Pollution Prevention Program 40 2.4.5 CCME Guidelines 40 2.5 Previous Research 42 2.5.1 Sediment Chemistry 42 2.5.2 Sedimentation Rates and Redox Conditions 44 2.5.3 Bioaccumulation of Contaminants 45 Chapter 3 Methods 48 3.1 Sample Collection 48 3.1.1 Vibracoring 48 3.1.2 Slow Coring and Gravity Coring 55 3.1.3 Grab Sampling 56 3.2 Inorganic Chemistry Analytical Protocols 57 3.2.1 Flame Atomic Absorption Spectroscopy 57 3.2.2 Graphite Furnace Atomic Absorption Spectroscopy 57 3.2.3 Solid State Atomic Absorption Spectroscopy 58 3.3 Organic Chemistry Analytical Protocols 60 3.3.1 Organic Carbon.. 60 3.3.2 Polycyclic Aromatic Hydrocarbons and Coprostanol. 61 3.4 Dating Techniques 63 3.4.1 210Pb Dating 63 3.4.2 137Cs Dating 64 3.5 Pore Water Chemistry Analytical Protocols 65 3.5.1 Ammonium 65 3.5.2 Sulphate 66 3.5.3 Salinity 66 Chapter 4 Results 67 4.1 Inorganic Chemistry of Marine Sediments 68 v 4.2 Organic Chemistry of Marine Sediments 78 4.2.1 Organic Carbon 78 4.2.2 Polycyclic Aromatic Hydrocarbons 78 4.2.3 Coprostanol 82 4.3 210Pb and 137Cs Dating of Marine Sediments . 84 4.4 Pore Water Chemistry of Marine Sediments 85 Chapter 5 Spatial and Temporal Changes in Marine Sediment Chemistry 86 5.1 Correlations Between Analytes 87 5.2 Redox Conditions in Harbour Sediments 89 5.3 Average and Present-Day Sediment Accumulation Rates 91 5.4 Temporal Variations in Marine Sediment Chemistry 93 5.4.1 Background Concentrations in Pre-industrial Sediments 93 5.4.2 Temporal Variations in Inorganic Contaminants 95 5.4.3 Temporal Variations in Organic Contaminants 99 5.5 Spatial Variations in Marine Sediment Chemistry 108 5.5.1 Spatial Variations in Inorganic Contaminants 108 5.5.2 Spatial Variations in Organic Contaminants 122 5.6 Summary 129 Chapter 6 Effects of Wastewater Treatment Practices on Marine Sediment Chemistry near Mill Cove, Bedford 131 6.1 Average and Present-Day Sediment Accumulation Rates 132 6.2 Variations in Inorganic Contaminants near Mill Cove 135 6.3 Variations in Organic Contaminants near Mill Cove 145 6.4 Anticipated Effects of Wastewater Treatment 149 6.5 Summary 152 Chapter 7 Conclusions 153 7.1 Summary of Conclusions 153 7.2 Suggestions for Future Research 155 References 157 Appendix A Sampling Summary 175 Appendix B Sediment Geochemical Results 179 Appendix C Geochemical Sediment Grab Sample Plots and Maps 211 Appendix D Sediment PAH and Steroid Results 218 VI Appendix E Geochemical Sediment Core Profiles 233 Appendix F Pore Water Results and Core Profiles 263 Appendix G 210Pb and 137Cs Results 267 Appendix H Core Description Logs and Photographs 272 vn LIST OF TABLES Table 1.1 PAH ratios as indicators of pyrogenic and petrogenic sources 17 Table 1.2 PAH ratios as indicators of hydrocarbon sources 17 Table 1.3 Sediment quality values of select metals and PAHs 24 Table 2.1 Total suspended solids in Halifax Harbour 30 Table 2.2 Removal efficiencies achieved through primary, advanced primary, and secondary wastewater treatment techniques 38 Table 2.3 Average influent concentrations, effluent concentrations, and removal efficiencies of select metals from the Mill Cove WWTF between 2003 and 2008 39 Table 3.1 List of analytical detection limits in marine sediments 58 Table 3.2 Analyzed parental PAHs, their abbreviations in brackets, their corresponding molecular weights, and number of aromatic rings 62 Table 3.3 Analyzed alkylated PAHs arranged according to degree of alkylation 62 Table 4.1 Summarized grab sample geochemical data 69 Table 4.2 Grab sample PAH summary data 80 Table 4.3 Sediment core PAH summary data 81 Table 5.1 Background concentrations of select contaminants 94 Table 5.2 Sediment core diagnostic PAH ratios 103 Table 5.3 Sediment core diagnostic steroid ratios 106 Table 5.4 Comparison of summarized geochemical data from sediment grab samples collected in 2008 - 2009 and 1986 - 1988 112 Table 5.5 Geochemical comparison of different sampling methods 121 Table 5.6 Comparison of background concentrations, sediment quality values, and median sediment grab sample concentrations 121 Table 5.7 Sediment grab sample diagnostic PAH ratios 125 Table 5.8 Sediment grab sample diagnostic steroid ratios 128 Table A.l Sampling summary 176 Table B.l Grab sample geochemical data 180 Table B.2 Sediment core geochemical data 183 Table B.3 Correlation coefficients (r) between organic contaminants and organic carbon in sediment core bottoms 209 Table B.4 Correlation coefficients (r) between inorganic contaminants and organic carbon in the top 10 cm of sediment cores and grab samples 210 vui Table D.l Sediment grab sample parental PAH results 219 Table D.2 Sediment grab sample alkylated PAH results 220 Table D.3 Sediment grab sample steroid results 221 Table D.4 Sediment core parental PAH results 222 Table D.5 Sediment core alkylated PAH results 226 Table D.6 Sediment core steroid results 230 Table D.7 Correlation coefficients (r) between PAHs, coprostanol, and organic carbon in sediment core tops and grab samples 232 Table F.l Pore water geochemistry results 264 Table G.l Sediment core 210Pb and 137Cs results 268 Table H.l Sediment core description of 1993 vibracore2 273 Table H.2 Sediment core description of 1993 vibracore 9 274 Table H.3 Sediment core description of 1993 vibracore 10 275 Table H.4 Sediment core description of 2008 vibracore 2 276 Table H.5 Sediment core description of 2008 vibracore 3 277 Table H.6 Sediment core description of 2008 vibracore 5 278 Table H.7 Sediment core description of 2008 vibracore 6 280 Table H.8 Sediment core description of 2008 vibracore 7 281 Table H.9 Sediment core description of 2008 vibracore 8 282 Table H.10 Sediment core description of 2008 vibracore 9 283 Table H.ll Sediment core description of gravity core 5 284 IX LIST OF FIGURES Figure 1.1 Map showing the locations of the major