Hamiltonharbourfieldseasonassessment,labencki,2008

2008 Field Season in the Hamilton Harbour Area of Concern

Hamilton Harbour PCB Assessment

Prepared by:

Tanya Labencki Environmental Monitoring and Reporting Branch

Ontario Ministry of the Environment

Prepared for:

Hamilton Harbour Remedial Action Plan Toxic Substances and Sediment Technical Team

March 2011

Page left intentionally blank for printing purposes

2008 Field Season in the Hamilton Harbour Area of Concern

Hamilton Harbour PCB Assessment

March 2011

Prepared by:

Tanya Labencki Environmental Monitoring and Reporting Branch

Ontario Ministry of the Environment

For: Hamilton Harbour Remedial Action Plan

Toxic Substances and Sediment Technical Team

2008 Field Season in the Hamilton Harbour Area of Concern Hamilton Harbour PCB Assessment Prepared by: Tanya Labencki

Environmental Monitoring and Reporting Branch Ontario Ministry of the Environment

For: Hamilton Harbour Remedial Action Plan Toxic Substances and Sediment Technical Team First Published: March 2011 ISBN: 978-0-9810874-5-0 (Print Version) ISBN: 978-0-9810874-6-7 (Online Version) For more information contact: Hamilton Harbour Remedial Action Plan Office P.O. Box 5050 867 Lakeshore Road Burlington, Ontario, L7R 4A6 Canada Tel. 905-336-6279 Email [email protected] Website: www.hamiltonharbour.ca/rap

2008 Field Season in Hamilton Harbour

Hamilton Harbour Remedial Action Plan iii

Executive Summary

In the Hamilton Harbour Area of Concern (AOC), the beneficial use impairment (BUI) Restrictions on Fish and Wildlife Consumption is driven by elevated concentrations of PCBs in sport fish. Although PCB concentrations in Hamilton Harbour sport fish tissue have declined over time, concentrations remain above the first consumption restriction level. Similar to sport fish trends, PCB concentrations in Harbour surface sediment have also declined over time, however concentrations in both the main basin (~500 ng/g) and Windermere Arm (~1,270 ng/g) remain high enough to predict biomagnification above consumption thresholds (Labencki, 2008).

In 2007, five event-based water surveys of Harbour inputs as well as three ambient water surveys in the Harbour were conducted to investigate whether PCBs in the Harbour are primarily historical in nature, or if there are any locally-controllable sources and potential remedial actions to be undertaken towards delisting the BUI (HH RAP, 2003). The results of the 2007 water sampling did not suggest the presence of a locally-controllable PCB source to the WWTPs and tributary stations monitored. More importantly however, the inflows characterized did not seem to be able to account for the PCB concentrations measured in the ambient waters of Windermere Arm – PCB concentrations were higher in the Harbour relative to inflow waters, a gradient reverse to that expected. Further supporting the lack of congruence between characterized Harbour inputs and ambient conditions was that the PCB congener signature of effluent from the Woodward Ave WWTP – the largest characterized Harbour PCB loading in 2007 (Labencki, 2009) – differed from the PCB congener signature of Windermere Arm water. These results suggested that either recirculation of historical PCB sources (i.e. sediment resuspension) and/or an uncharacterized source of PCBs was driving elevated PCB concentrations in the waters of Hamilton Harbour. As potential remedial actions for each of these scenarios differs, follow-up action included a comprehensive PCB survey of the Harbour during 2008.

In 2008, water samples were collected at 9 stations in Hamilton Harbour: 1. Station 09 01 0258 – Centre Station 2. Station 09 01 0268 – Windermere Arm/Basin Bridge 3. Station 09 01 0352 – Windermere Arm Centre Station 4. Station 09 01 0365 – south shore of the main basin near Randle Reef 5. Station 09 01 0366 – Strathearne Avenue Slip (south end) 6. Station 09 01 0367 – west end of main basin near Desjardins Canal 7. Station 09 01 0368 – north shore of the main basin near LaSalle Marina 8. Station 09 01 0369 – ArcelorMittal Dofasco Boat Slip (mid-Slip) 9. Station 09 01 0370 – mouth of Windermere Arm near Pier 27

Five water surveys were conducted between May and September 2008 where at each station, two water samples were collected: a surface depth-integrated sample and a grab sample 1 m from the sediment bed. QA/QC procedures included field blanks, duplicate samples and a paired comparison between surface-integrated and bottom


Hamilton Harbour Remedial Action Plan iv

sampling grab methods. All water samples were analyzed by the MOE for PCBs (82 congeners) and TSS.

In conjunction with water sampling, semi-permeable membrane devices (SPMDs) were deployed at all 9 water sampling stations, as well as one additional station in Cootes Paradise (station 09 01 0371 – east end of Cootes Paradise near the Desjardins Canal). Three SPMDs were deployed in a metal shroud mid-water column at each station for two discrete 28-day deployments (June and August, 2008). QA/QC procedures included one field blank per SPMD deployment and lab blanks. All sample, trip and lab blank SPMDs were analyzed by Trent University for PCBs (33 congeners). Timing of the water sampling coincided with timing of the SPMD deployment and retrievals. Also during the 2008 season in Hamilton Harbour, primary sludge was collected on two occasions (June and August, 2008) from the Dundas (station 09 03 0003), Skyway (station 09 03 0005) and Woodward Avenue (station 09 03 0004) waste water treatment plants (WWTPs) and analyzed by the MOE for total PCBs. Additionally during 2008, three event-based water surveys (two wet, one dry) were conducted at one station in Chedoke Creek (09 15 0010) between May and August 2008. Water samples were grab samples and were analyzed by the MOE for PCBs (82 congeners) and TSS. Also in 2008, one surface sediment grab sample was collected with a ponar sampler from the Strathearne Slip (station 09 01 0366) during August 2008. The sediment was homogenized and analyzed by the MOE for PCB congeners (55 congeners), PAH compounds (18 compounds) and total organic carbon (TOC). Young-of-the-year (YOY) fish were also to be sampled during the 2008 field season, but sampling was forfeited due to a lack of fish found during sampling attempts.

The results of the 2008 Harbour water sampling and SPMD deployments were consistent in that both media demonstrated strong and similar spatial gradients among stations sampled. The average PCB concentrations in water in the main basin of the Harbour (stations 367, 365, 258, 368) were similar at ~4 ng/L; the average PCB concentration increased approximately 5 fold towards Windermere Arm (~20 ng/L; station 352) and another 5 fold again in the two slips monitored (~100 ng/L; stations 369, 366). The single highest PCB concentration in water measured in 2008 was 387 ng/L, a surface depth-integrated sample from station 366 on August 19. This concentration was two orders-of-magnitude above Harbour background levels. In addition, while PCB concentrations at stations in the main basin of the Harbour remained relatively stable among surveys, large temporal variability was observed for stations in Windermere Arm (352, 369, 268, 366), suggesting intermittent PCB inputs.

While monitoring PCB concentrations in water has direct environmental relevance, these measurements are instantaneous unlike SPMDs which provide an indication of conditions throughout the entire deployment period. The average PCB concentration in SPMDs deployed in Cootes Paradise were approximately ~150 ng/mL triolein, increasing towards the main basin of the Harbour where concentrations at all stations were similar at ~400 ng/mL triolein; the average PCB concentration increased


Hamilton Harbour Remedial Action Plan v

approximately 5 fold towards Windermere Arm (~1,900 ng/mL triolein) and another 7 fold again at station 366 (~13,000 ng/mL triolein). The single highest concentration measured in 2008 was 23,000 ng/mL triolein from one of the replicates at station 366 during the August deployment. Average PCB concentrations in SPMDs deployed at station 366 were approximately 3 fold higher than the highest concentrations observed in the MOEs PCB trackdown program.

Similar to total PCB concentrations, PCB congener patterns observed in water and SPMDs during 2008 were also consistent in that similar PCB congener patterns at each station were observed for both media. Generally, PCB congener patterns at station 268, and station 366 in particular, were enriched in less-chlorinated biphenyls; and PCB congener patterns at station 369 were enriched in more-chlorinated biphenyls relative to other stations in the Harbour. Also, while the PCB congener pattern at stations in the main basin of the Harbour showed little variability between stations, some variability in PCB congener patterns among stations and surveys was observed for stations in Windermere Arm providing further lines-of-evidence on PCB dynamics in this area of the Harbour.

During the August 19, 2008 water survey, total PCB concentrations were elevated at Windermere Arm stations, especially at station 366 where an enrichment of tri-chlorinated biphenyls was also observed relative to other surveys. Further, an enrichment of tri-chlorinated biphenyls was also observed as a decreasing gradient towards “downstream” areas during the August survey, suggesting contribution of this source to other areas of the Harbour. Also, most stations showed relatively higher total PCB concentrations in SPMDs and higher proportions of tri-chlorinated biphenyls during the August SPMD deployment, suggesting a build-up of the less-chlorinated PCB source during the summer stratification period. Like water, SPMDs deployed at station 366 as well as 268 were also enriched in tri-chlorinated biphenyls relative to other stations, suggesting that the PCB pattern observed in water on August 19 was not an isolated incident. The PCB congener pattern observed at stations 268 and 366 was also found to be very similar to the pattern observed in Woodward Ave WWTP effluent sampled in 2007, suggesting that the CSOs in the southeast corner of the Harbour may be a conduit for PCBs to the Harbour. The results of sewage sludge sampling from the three WWTPs demonstrated that mean PCB concentrations in primary sewage sludge were 87 ng/g dw, 330 ng/g dw and 78.5 ng/g dw from the Dundas, Woodward and Skyway WWTPs, respectively. Total PCB concentrations from the Woodward Avenue WWTP were three to five fold higher than concentrations at the Dundas and Skyway WWTPs, suggesting that the Hamilton sewershed remains the primary PCB source area relative to the Dundas and Burlington sewersheds.

The results of the event-based water sampling in Chedoke Creek demonstrated total PCB concentrations between 3-4 ng/L in the Creek, consistent with concentrations observed in other Hamilton area creeks monitored during 2007 and not suggestive of a local PCB anomaly.


Hamilton Harbour Remedial Action Plan vi

The results of the surface sediment sampling at station 366 in the Strathearne Avenue Slip demonstrated total PCB concentrations of ~16,000 ng/g dw, over an order-of-magnitude greater than average PCB concentrations in Windermere Arm sediment. Also, the PCB congener pattern had a higher proportion of less-chlorinated congeners relative to the Windermere Arm sediment. The total PAH concentration of the sediment sample was extremely high with a total PAH concentration of ~5,700 ug/g or approximately 0.5% PAH. This PAH concentration is on par with PAH concentrations observed in Randle Reef sediment and is six times the severe effect level (SEL) (MOE, 1993). It is suspected that sediment contamination characterized at station 366 during 2008 may be related to the persistent oil sheens observed in the southern half of the Strathearne Ave Slip during the 2008 monitoring season.

Analysis of multi-media data collected during the 2008 field season in Hamilton Harbour resulted in several important conclusions relevant to the Hamilton Harbour RAP: 1. Multiple lines-of-evidence collected during 2008 including spatial gradients observed

for PCB concentrations in both water and SPMDs, as well as patterns in temporal variability and PCB congener signatures, suggested that Windermere Arm remains the primary PCB source area to Hamilton Harbour.

2. Resuspension of PCB-contaminated sediment is likely occurring periodically throughout Windermere Arm to maintain high background levels of PCB in the water column throughout the Harbour.

3. Episodic inputs of significant, external PCB source(s) may be entering the Harbour via the Windermere Basin, the ArcelorMittal Dofasco Boat Slip, and particularly the Strathearne Avenue Slip.

4. Persistent oil sheens and anomalously high PCB and PAH concentrations in sediment were found in the Strathearne Avenue Slip.

5. Data did not support the presence of an ongoing, local source of PCB to the main basin of the Harbour and thus follow-up PCB trackdown investigations in the main basin of the Harbour are not warranted.

6. Data did not support the presence of an ongoing, local source of PCBs to Cootes Paradise, including Chedoke Creek, and thus follow-up PCB trackdown investigations in Cootes Paradise and Chedoke Creek are not warranted.

7. The enrichment of less-chlorinated PCB congeners in water from the Strathearne Avenue Slip and the Windermere Basin may be responsible for a greater bioavailablity of PCBs in the water column of Hamilton Harbour relative to a PCB congener signature consisting of more-chlorinated PCB congeners.

In addition, as follow-up to the sampling conducted in Hamilton Harbour during

2008, several recommendations have been formed to advance actions towards delisting the relevant BUI under the Hamilton Harbour RAP. These recommendations include: 1. Water from the Parkdale, Strathearne Ave and Kenilworth CSOs should be sampled

during overflow events to determine if these CSOs are conveying an ongoing, active


Hamilton Harbour Remedial Action Plan vii

source of PCBs to the Windermere Basin, Strathearne Avenue Slip and ArcelorMittal Dofasco Boat Slip, respectively.

2. Sediment cores should be collected along a north-south transect in the Strathearne Avenue Slip to determine the extent and nature of sediment contamination in the Slip.

3. An ADCP current meter should be installed in the Strathearne Avenue Slip to estimate PCB loads from the Slip and help evaluate if the Strathearne Ave Slip is overall a source or sink of PCB contamination in context of Windermere Arm.

4. YOY fish sampling should be re-attempted in 2009 at the locations sampled in 2006 (Grindstone Creek, CCIW) to determine if elevated PCB concentrations observed in 2006 were part of the natural variability or if biological exposure to PCBs has increased in recent years.

5. Any follow-up on further understanding PCB fate and transport mechanisms in the Harbour should focus on Windermere Arm, where differences in spatial trends both for total PCB concentrations and PCB congener signatures are more pronounced relative to the main basin of the Harbour.

6. Work should continue on implementing the sediment management strategy for contaminated sediment in the ArcelorMittal Dofasco Boat Slip.

7. Mitigation measures should be examined to determine if they are necessary for reducing sediment resuspension due to the passage of vessels in areas of high sediment contamination, e.g. Windermere Arm. To assist with this determination, sediment traps should be deployed in key locations.

Interpretation of Harbour-wide PCB dynamics remains complex; however, both

resuspension processes and ongoing inputs may be contributing towards elevated PCB concentrations in Harbour surface sediment and water, and subsequently, elevated PCB concentrations in sport fish. Future investigations will continue to be conducted within the context of the BUI Restrictions on Fish and Wildlife Consumption to determine what remedial actions should or can be taken to address any locally-controllable sources of PCBs in order to ultimately delist Hamilton Harbour as an AOC.


Hamilton Harbour Remedial Action Plan viii

Acknowledgements

Many people were instrumental to the completion of work described herein, and their assistance and cooperation are greatly appreciated. Many thanks are extended to the Great Lakes Unit (Ministry of the Environment (MOE)) field crew who collected the Harbour water samples and deployed the semi-permeable membrane devices (SPMDs) in the Harbour: Ryan Adams, Nathan Brandt, Greg Hobson, Wendy Page, and Travis Nunnamaker. This work could not have been conducted without the capable help and skills of Brian Thorburn of West Central Region (WCR), Hamilton Regional Office (MOE), who operated the Great Lakes Guardian for this 2008 field work; additional assistance from WCR is also appreciated for field work (Ron Hall, Lindsey Burzese, Taylor and Holly), report review (Sarah Day) and ongoing RAP support (Mary Ellen Scanlon, Cheriene Vieira). Many thanks are also extended to Dave Supper (Great Lakes Unit, MOE) for collection of samples from Chedoke Creek and the wastewater treatment plants (WWTPs). Additionally, thanks are extended to Eric Reiner and colleagues of the Dioxins and Toxics Organics Unit of the Laboratory Services Branch (MOE) for analytical assistance, and Duncan Boyd, Nadine Benoit and Paul Helm, all of the Great Lakes Unit (MOE) for ongoing assistance with project planning and/or interpretation. Assistance from individuals external to the MOE was also key to completion of the 2008 field season, particularly Chris Metcalfe and Tracy Metcalfe of Trent University who prepared, analyzed and assisted with interpretation of the SPMDs. Further to this, Debbie Burniston of Environment Canada is gratefully acknowledged for administrating the Environment Canada contract which funded the second round of SPMDs deployed in the Harbour (“Deployment 2”), and also for providing the Ottawa Street Slip sediment data along with Chris Marvin, also of Environment Canada. Thanks are also extended for the support provided by Mukesh Patel of the Regional Municipality of Halton for sampling at the Skyway WWTP, to Ian Routledge, Walter Furry and Richard Fletcher of the City of Hamilton for sampling at the Woodward Ave and Dundas WWTPs, to Jennifer Bowman and Tys Theysmeyer of Royal Botanical Gardens (RBG) for sampling in Cootes Paradise, and to Sarodha Rajkumar and Peter Cegnar for sampling in the ArcelorMittal Dofasco boat slip.

The Hamilton Harbour Remedial Action Plan (HH RAP) Office as well as the HH RAP Toxic Substances and Sediment Technical Team are also acknowledged for their ongoing support as well as comments provided by Kristin O’Connor (HH RAP Office), Matt Graham (Environment Canada) and Sarodha Rajkumar (ArcelorMittal Dofasco).


Hamilton Harbour Remedial Action Plan ix

Table of Contents Executive Summary ........................................................................................................iii Acknowledgements .......................................................................................................viii Table of Contents............................................................................................................ix List of Figures..................................................................................................................xi List of Tables.................................................................................................................xiv 1. Background ................................................................................................................. 1

1.1 Follow-up of 2007 Field Season Recommendations .............................................. 4 1.1.1 Determination of an active, locally-controllable source of PCBs....................... 4 1.1.1.1 Literature Review of Potential PCB Sources in the Hamilton Harbour Watershed................................................................................................................. 6 1.1.2 Resuspension of PCB-Contaminated Sediment............................................. 18 1.1.3 Follow-up to determine source of PCBs measured at the Desjardins Canal .. 20 1.1.4 Follow-up to determine recent PCB exposure by YOY fish ............................ 20

1.2 2008 Field Season Objectives............................................................................. 21 1.3 2008 Field Season Limitations ............................................................................ 22

2. Methods .................................................................................................................... 24 2.1 Water sampling in Hamilton Harbour.................................................................... 24 2.2 Semi-permeable membrane device (SPMD) deployment in Hamilton Harbour.... 27 2.3 Waste water treatment plant (WWTP) primary sludge sampling .......................... 33 2.4 Event-based water sampling in Chedoke Creek................................................... 34 2.5 Sediment sampling in Strathearne Avenue Slip ................................................... 35 2.6 Young-of-the-year (YOY) fish sampling................................................................ 36

3. Results and Discussion ............................................................................................. 37 3.1 General Field Observations.................................................................................. 37 3.2 Water Sampling in Hamilton Harbour ................................................................... 43

3.2.1 Quality Assurance/Quality Control of Water Samples .................................... 43 3.2.2 Total PCB Water Concentrations ................................................................... 48 3.2.3 TSS Water Concentrations............................................................................. 51 3.2.4 TSS-Total PCB Correlations and Regressions............................................... 54 3.2.5 Theoretical PCB Concentration on Suspended Sediment and Comparison to Surface Sediment.................................................................................................... 57 3.2.6 Variability of Total PCB Concentrations with Depth in the Water Column at Each Station............................................................................................................ 60 3.2.7 Temporal Variability in PCB and TSS Concentrations.................................... 70 3.2.8 Spatial Variability of PCB Water Concentrations in the Harbour .................... 74 3.2.9 Examination of PCB Anomalies and Potential PCB Sources in the Harbour.. 82

3.3 Semi-Permeable Membrane Device (SPMD) Deployment in Hamilton Harbour .. 92 3.3.1 Quality Assurance/Quality Control (QA/QC) of SPMD Deployments.............. 92 3.3.2 Total PCB Concentrations in SPMDs ............................................................. 97 3.3.3 Temporal Variability in PCB SPMD Concentrations ..................................... 100


Hamilton Harbour Remedial Action Plan x

3.3.4 Spatial Variability in Total PCB Concentrations in SPMDs........................... 106 3.3.5 Implications of 2008 SPMD and Water Sampling......................................... 115

3.4 WWTP primary sludge sampling ........................................................................ 118 3.5 Event-based water sampling in Chedoke Creek................................................. 120 3.6 Sediment Sampling in the Strathearne Avenue Slip........................................... 127

4. Conclusions............................................................................................................. 131 5. Recommendations .................................................................................................. 136 6. References.............................................................................................................. 140 Appendix I: May – September 2008 weather conditions in Hamilton .......................... 145 Appendix II: MOE Analytical Methods ......................................................................... 150 Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods154 Appendix IV: Water Column Profiles and Sampling Depths at Nine Stations for Five Water Quality Surveys................................................................................................. 157 Appendix V: Qualitative field notes on condition of metal shrouds and external surface of SPMDs upon retrieval ............................................................................................. 170 Appendix VI: Tidbit Temperature Data for Ten Stations and Two SPMD Deployments.................................................................................................................................... 171


Hamilton Harbour Remedial Action Plan xi

List of Figures Figure 1: Location of Windermere Arm in Hamilton Harbour........................................... 1 Figure 2: Mean PCB concentrations measured at all Hamilton Harbour stations monitored during 2007. ................................................................................................... 3 Figure 3: Map of water sampling locations for 2008 field season in Hamilton Harbour . 25 Figure 4: Instrumentation used to collect water samples during 2008 field season in Hamilton Harbour: depth-integrated samples were collected with a glug-glug water sampler (left) and grab water samples were collected with a beta bottle (right). ........... 26 Figure 5: SPMD deployment locations for 2008 field season in Hamilton Harbour ....... 29 Figure 6: Photograph of SPMDs being wired to the inside of a metal shroud used to house the SPMDs at each station. Also shown is the Viny float (orange sphere) used to keep the SPMD assembly buoyant in the water column. .............................................. 30 Figure 7: General installation set-up of SPMDs in the water column (Figure created by Wendy Page, Great Lakes Unit).................................................................................... 31 Figure 8: Installation set-up of SPMDs at station 371 in Cootes Paradise .................... 32 Figure 9: Sludge sampling locations for the 2008 field season in Hamilton Harbour..... 33 Figure 10: Water sampling location in Chedoke Creek for 2008 field season. .............. 34 Figure 11: Sediment sampled August 19, 2008 from station 366 in the Strathearne Avenue slip.................................................................................................................... 36 Figure 12: Boom at Strathearne Ave Slip CSO outfall – southwest corner of the Strathearne Ave Slip. .................................................................................................... 37 Figure 13: Select photographs of oil sheens observed on the surface of the water at Station 366 during the 2008 field season: June 3 (top left), June 4 (bottom left), September 17 (top right), September 18 (bottom right)................................................. 38 Figure 14: Dreissenid mussels caught on the anchor from Station 370 on May 28, 2008....................................................................................................................................... 39 Figure 15: Sediment plumes observed in the Harbour on August 19, 2008 in: the northeast corner of the Harbour (left) and at the west end of the Harbour near the mouth of the Grindstone Creek and the Desjardins Canal (right)............................................. 40 Figure 16: Blue-green algae bloom at Station 258 on August 20, 2008. ....................... 40 Figure 17: Algae blooms observed in the Harbour on September 17, 2008: at the CCIW dock (top left), near Station 268 (top right) and on piece of SPMD shroud removed from Station 366 (bottom left). ............................................................................................... 41 Figure 18: Photographs of algae blooms at Station 366 on September 18, 2008. ........ 42 Figure 19: Correlation between total PCB concentration in field blanks and total PCB concentration in sample at station of field blank collection. ........................................... 44 Figure 20: PCB congener patterns for four field blanks collected during summer 2008 relative to PCB congener patterns for Aroclors and water samples from station where field blank was collected................................................................................................ 45 Figure 21: Regression analysis of paired Glug Glug-Beta Bottle water samples collected from 0.5 m depth at various stations in Hamilton Harbour during the 2008 field season.


Hamilton Harbour Remedial Action Plan xii

...................................................................................................................................... 47 Figure 22: PCB congener profiles for paired water samples collected at 0.5 m depth using beta bottle and Glug Glug samplers to examine potential bias between sampling methods ........................................................................................................................ 48 Figure 23: Mean total PCB concentrations for each station and sample type for five water surveys during summer 2008. ............................................................................. 50 Figure 24: Mean TSS concentrations for each station and sample type for five water surveys during summer 2008. ....................................................................................... 52 Figure 25: Correlation between TSS and PCB concentration at each station for five surveys during summer 2008. ....................................................................................... 56 Figure 26: Theoretical PCB concentrations on suspended sediment relative to measured PCB concentrations in surface sediment...................................................... 57 Figure 27: PCB congener patterns for two sample types at each station during five surveys conducted during 2008 relative to Aroclor and sediment PCB congener profiles....................................................................................................................................... 65 Figure 28: Temporal trends of PCB concentrations at each station monitored during 2008 .............................................................................................................................. 73 Figure 29: Principle Component Analysis (PCA) plots for water samples collected during each survey in 2008 relative to Aroclor mixtures. .......................................................... 81 Figure 30: PCB homolog profiles for station 366 water, station 366 sediment, and final effluent from the Woodward Ave WWTP relative to Aroclor profiles ............................. 84 Figure 31: PCB congener profiles for water samples from station 268, station 366, and the Woodward Ave WWTP relative to Aroclor profiles. ................................................. 86 Figure 32: PCB homolog profiles for water samples collected from station 268 in 2008 relative to 1984.............................................................................................................. 87 Figure 33: PCB homolog profiles for water and sediment samples collected from station 352 ................................................................................................................................ 89 Figure 34: PCB homolog profiles for water and sediment samples collected from station 258 ................................................................................................................................ 91 Figure 35: PCB congener profile for the August 2008 Station 370 field blank relative to Station 370 samples and an Aroclor profile................................................................... 95 Figure 36: Mean water temperature (°C) at depth of SPMD deployment at each station during each of the two deployment periods................................................................... 96 Figure 37: PCB concentrations in SPMDs deployed in Hamilton Harbour during 2008. 97 Figure 38: PCB concentrations in SPMDs deployed in Hamilton Harbour during 2008 relative to PCB concentrations measured at other nearshore locations in the lower Great Lakes during 2006 and 2007. .............................................................................. 98 Figure 39: Mean PCB concentrations in SPMDs deployed in Hamilton Harbour during 2008 relative to maximum PCB concentrations in SPMDs from Project Trackdown. .... 99 Figure 40: PCB concentrations in SPMDs deployed at station 258 in 2006 and 2008.102 Figure 41: Daily precipitation measured in Hamilton during both SPMD deployment periods during summer 2008....................................................................................... 103 Figure 42: PCB congener patterns for all replicate SPMDs deployed at each station during two deployment periods ................................................................................... 105


Hamilton Harbour Remedial Action Plan xiii

Figure 43: Principle Component Analysis (PCA) plots for SPMDs during each deployment in 2008 relative to Aroclor mixtures.......................................................... 111 Figure 44: Homolog patterns for water samples and SPMDs deployed at stations 268 and 366 relative to the homolog pattern for effluent from the Woodward Ave WWTP 114 Figure 45: PCB concentrations in YOY fish over time in Hamilton Harbour (upper; 5 locations) and Lake Ontario (lower) ............................................................................ 116 Figure 46: PCB congener profiles of fathead minnow tissue from 3-week exposure bioassays conducted on surface sediment from Windermere Arm. ............................ 117 Figure 47: Mean 2008 total PCB concentration in Chedoke Creek relative to mean 2007 total PCB concentration in other Hamilton Harbour tributaries (Labencki, 2009). ....... 122 Figure 48: PCB congener profiles for three 2008 Chedoke Creek surveys ................. 123 Figure 49: PCB congener patterns of seven Aroclors ................................................. 124 Figure 50: PCB congener patterns observed 2008 in Chedoke Creek relative to patterns observed at the Desjardins Canal and Hamilton Harbour Centre Station in 2007....... 125 Figure 51: Principle Component Analysis (PCA) plot for water samples collected during 2008 from Chedoke Creek relative to water samples collected during 2007 at Centre Station and at the Desjardins Canal. ........................................................................... 126 Figure 52: PCB congener patterns in a) Strathearne Ave Slip surface sediment; and b) Windermere Arm surface sediment. ............................................................................ 128 Figure 53: PAH compound profile for surface sediment from Station 366 in Strathearne Ave Slip. ...................................................................................................................... 130


Hamilton Harbour Remedial Action Plan xiv

List of Tables Table 1: Water sampling locations for 2008 field season in Hamilton Harbour. ............ 24 Table 2: Station locations of QA/QC samples collected during the 2008 field season in Hamilton Harbour .......................................................................................................... 27 Table 3: SPMD deployment locations for 2008 field season in Hamilton Harbour. ....... 28 Table 4: Depth of SPMD deployment (m below surface) at each station during each 2008 deployment period................................................................................................ 30 Table 5: Primary sludge sampling locations for 2008 field season in Hamilton Harbour33 Table 6: Results of QA/QC field blank total PCB concentration data for summer 2008 water sampling in Hamilton Harbour. ............................................................................ 43 Table 7: PCB and TSS replicate results and calculated coefficient of variation (CV) .... 46 Table 8: Total Σ82PCB concentrations (ng/L) for water samples collected from Hamilton Harbour during summer 2008 ....................................................................................... 49 Table 9: TSS concentrations (mg/L) for water samples collected from Hamilton Harbour during summer 2008 ..................................................................................................... 53 Table 10: TSS-PCB regression equations by station .................................................... 54 Table 11: Theoretical PCB concentrations on suspended sediment for five surveys conducted during summer 2008.................................................................................... 58 Table 12: Matched paired t test for two sample types at each station during summer 2008 .............................................................................................................................. 61 Table 13: Variability in PCB and TSS concentrations in the water column expressed as a ratio of the highest concentration to the lowest concentration at each station for the five surveys conducted during summer 2008. ............................................................... 70 Table 14: Mann-Whitney pairwise comparison uncorrected (upper right) and Bonferroni corrected (lower left) p-values for a) Surface-integrated samples and b) Bottom grab samples......................................................................................................................... 75 Table 15: Stations between which no significant difference in total PCB concentrations was determined according to the Mann-Whitney pairwise comparisons ....................... 76 Table 16: Total PCB concentrations (ng/mL triolein or ng/SPMD) in all SPMDs deployed in Hamilton Harbour during 2008. ................................................................................. 93 Table 17: Total PCB concentrations (ng/mL triolein or ng/SPMD) in SPMD field blanks...................................................................................................................................... 94 Table 18: Temporal variability of PCB concentrations in SPMDs as measured as a ratio of the two deployments during summer 2008.............................................................. 100 Table 19: Mann-Whitney pairwise comparison uncorrected (upper right) and Bonferroni corrected (lower left) p-values for total PCB concentrations in SPMD replicate samples..................................................................................................................................... 107 Table 20: Stations between which no significant difference in total PCB concentrations in replicate SPMDs was determined according to the Mann-Whitney pairwise comparisons................................................................................................................ 107 Table 21: Total PCB concentrations (ng/g dry weight) measured in primary sewage


Hamilton Harbour Remedial Action Plan xv

sludge from three WWTPs during two surveys in 2008............................................... 118 Table 22: Results of 2008 water sampling in Chedoke Creek, station 09 15 0010 ..... 121


Hamilton Harbour Remedial Action Plan 1

1. Background

In the Hamilton Harbour Area of Concern (AOC), the Beneficial Use Impairment (BUI) Restrictions on Fish and Wildlife Consumption is driven by elevated levels of polychlorinated biphenyls (PCBs) in sport fish. As bioaccumulation and biomagnification of PCBs from surface sediment is a well known source of PCBs in sport fish, the sediment quality of the Harbour remains tied to this BUI. Particularly problematic is Windermere Arm (Figure 1), an area of Hamilton Harbour well known for its highly elevated levels of PCBs in sediment. Sediment cores sampled from Windermere Arm in 2003 (Environment Canada/Ministry of the Environment) as a follow-up to cores sampled in 2001 (Environment Canada) had total PCB concentrations in sediment up to 28 000 ng/g at 40 – 50 cm depth, and an area-averaged surficial (top 10cm) sediment PCB concentration of 1,270 ng/g (Labencki, 2008). These concentrations are well above the CCME (2001) Probable Effect Level (PEL) of 277 ng/g and the provincial Lowest Effect Level (LEL) of 70 ng/g (MOE, 1993).

Figure 1: Location of Windermere Arm in Hamilton Harbour. Despite the theoretical PCB pathway from sediment to sport fish in Hamilton Harbour as a whole, little was known on the specifics of how PCBs from Windermere Arm sediment in particular played into the observed high concentrations of PCBs in sport fish tissue. Further, it was unclear if Windermere Arm acted as a source or sink of PCB-contaminated sediment for the rest of the harbour. As a response to these unknowns, a PCB mass-balance model was constructed by researchers at the University of Toronto (Gandhi and Diamond, 2005). Due to uncertainty in PCB loading estimates and in-harbour concentration data required by the model, a sampling campaign was conducted by EMRB in 2007 to address this data gap.



The 2007 sampling campaign in Hamilton Harbour included both shore-based and in-Harbour components. The shore-based portion of the campaign was event-based and whole-water samples were collected from: three tributaries (Red Hill Creek, Indian Creek, Grindstone Creek); the Desjardins Canal; and final effluent from two waste water treatment plants (WWTPs). These locations were sampled on six occasions between March and September, 2007; events sampled included spring freshet, baseflow and four different sized storm events. For the in-harbour portion of the 2007 sampling campaign, depth-integrated whole-water samples were taken from the centre of the harbour (station 258) and Windermere Arm (station 352) in April, May and July 2007. These sampling surveys were pre-planned and did not correspond to the shore-based sampling events. All water samples were analyzed for PCB congeners (MOE congener method PCBC3459) and total suspended solids (TSS; MOE method SS3188).

A key result of the 2007 Hamilton Harbour sampling campaign was that in-Harbour PCB water concentrations were on par with or greater than those measured in the tributaries and WWTPs (Figure 2). Estimated PCB loads to the harbour from the inflows characterized in 2007 (two WWTPs, 3 tributaries) did not support the presence of a locally-controllable, active PCB source, and also did not seem to be able to explain the in-Harbour PCB concentrations observed given the process of dilution from inflows to receiver. Also, PCB concentrations in depth-integrated water samples were greater in Windermere Arm relative to the centre of the Harbour. Concentrations in the centre of the Harbour demonstrated relatively small temporal variability and were similar to those measured at the Desjardins Canal. PCB water concentrations in Windermere Arm, however, demonstrated greater relative variability and almost doubled between the May to July sampling events. An increase in TSS alone did not seem to be a primary explanatory factor for this phenomenon as the May and July TSS concentrations were similar.



0

5

10

15

20

25

WoodwardAvenueWWTP

SkywayWWTP

Red HillCreek

Indian Creek GrindstoneCreek

DesjardinsCanal

HamiltonHarbour

centre station

Mid-Windermere

Arm

Mea

n PC

B c

once

ntra

tion

(ng/

L)

Figure 2: Mean PCB concentrations measured at all Hamilton Harbour stations monitored during 2007. Notes: Error bars represent plus and minus one standard deviation of all 2007 surveys. Mean PCB concentrations are minimum PCB concentrations which were calculated assuming any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was equal to zero. Data source: Labencki, 2009. The 2007 results suggested the potential for relatively high pelagic exposure to PCBs, and on-going high benthic PCB exposure through deposition of PCBs from the water column to surface sediment. Further to this, PCBs in Hamilton Harbour sport fish have not likely declined to acceptable levels either due to: 1) the presence of an active PCB source to the Harbour which was not characterized through the inflows sampled in 2007; and/or 2) high resuspension rates maintaining high PCB concentrations in surface sediment and the water column through efficient recirculation of historical PCB contamination from the sediments.



1.1 Follow-up of 2007 Field Season Recommendations A number of recommendations were made following the 2007 field work to further the understanding of PCB dynamics in Hamilton Harbour. These recommendations were centred on gathering additional data to ultimately suggest what, if any, remedial actions are necessary to be able to delist the BUI Restrictions on Fish and Wildlife Consumption. The PCB-related recommendations of the 2007 field season included follow-up field work and sampling to determine if:

1. “there is an active, locally-controllable source of PCBs to Hamilton Harbour, and if an active source is the primary driver behind elevated PCB water concentrations in Hamilton Harbour, relative to resuspension” (Labencki, 2009, p.87);

2. “resuspension of PCB-contaminated sediment is a primary driver behind elevated PCB water concentrations in Hamilton Harbour” (Labencki, 2009, p.88);

3. “elevated PCB concentrations measured at the Desjardins Canal during 2007 represent flow from Hamilton Harbour, or an uncharacterized PCB source to Cootes Paradise” (Labencki, 2009, p.88);

4. “elevated PCB YOY fish concentrations observed in 2006 represent an increasing trend in PCB exposure in Hamilton Harbour” (Labencki, 2009, p.88).

1.1.1 Determination of an active, locally-controllable source of PCBs Following the finding that PCB concentrations in the Harbour were on par with or greater than PCB concentrations in Harbour inflows during 2007, a recommendation was made to follow-up on whether an active, locally-controllable source of PCB is potentially present in the Harbour. This recommendation was worded as follows in the HH RAP report summarizing the 2007 field season in Hamilton Harbour:

Follow-up field work and sampling should be conducted to determine if there is an active, locally-controllable source of PCBs to Hamilton Harbour, and if an active source is the primary driver behind elevated PCB water concentrations in Hamilton Harbour, relative to resuspension. Due to the anomalously high PCB concentrations measured in Windermere Arm water during 2007, subsequent investigations should focus spatially on Windermere Arm, although a Harbour-wide investigation should be completed for due diligence and the historical call for such actions. This recommended Harbour-wide PCB investigation into the potential presence of an active source should also focus on potential sources not investigated during 2007, that is, potential sources other than the Woodward Ave WWTP, Skyway



WWTP, Red Hill Creek, Indian Creek and Grindstone Creek. A full literature review should be conducted for identification of potential PCB sources in the Hamilton Harbour watershed, and following this, the field investigation and sampling should include coverage of these potential sources. A combination of media should be used in the investigation, such as grab water samples and semi-permeable membrane devices (SPMDs); the former sample type has direct environmental relevance and meaning, while the latter allows for a time-integrated picture of conditions between sampling events. (Labencki, 2009, p. 87).

In addition to the 2007 field work recommendation, follow-up action is also warranted given that the Hamilton Harbour RAP has long recognized the necessity of fully assessing any active, locally-controllable PCB sources to the Harbour as an act of due diligence in delisting. Many reports written both before and after the formation of the HH RAP in 1992 have recommended that an investigation be undertaken to evaluate all potential PCB sources to the Harbour. For example, in a full review on the chemical contamination of Hamilton Harbour, research was recommended to “[i]dentify all sources of PCBs” (Harlow and Hodson, 1988, p.75). Also, the HH RAP Stage 1 Report stated that:

PCBs in the water column require more thorough investigation in conjunction with analyses of sediments, rainfall, and biota to ensure that all possible remedial actions have been taken to eliminate local sources. Initial results (Fox, personal communication) indicate that PCBs in the Harbour are older, weathered components which have not been recently released to the environment (HH RAP, 1992, p.171).

In addition, the HH RAP 1998 Status Report stated that:

fish consumption advisories are based on PCBs and it is assumed there are no active sources, but there has been no full investigation to confirm this assumption (HH RAP, 1998, p.56) and that for substances which give rise to fish consumption advisories…no comprehensive investigation has been taken to determine whether local sources exist and may be controllable (HH RAP, 1998, p.57).

A comprehensive PCB monitoring program in potential source areas in Hamilton Harbour will address the assumptions which have been made to date regarding PCBs in Hamilton Harbour, and allow the HH RAP to move forward in the next step towards delisting the BUI Restrictions on Fish and Wildlife Consumption. Although a Harbour-



wide investigation of PCBs in Harbour inflows was undertaken from 1988-1991 by the MOE (Boyd, 2001), results are dated, only suspended sediment were analyzed rather than whole water samples, and potentially important CSO receiving areas were not investigated. A full investigation on the potential presence of active, locally-controllable sources of PCBs to Hamilton Harbour had yet to be conducted, so follow-up actions to the recommendation to assess potential PCB sources were pursued in the 2008 field season. The selection of sampling stations in 2008 reflected a literature review of potential PCB source areas in the Hamilton Harbour watershed.

1.1.1.1 Literature Review of Potential PCB Sources in the Hamilton Harbour Watershed Prior to selection of stations to be sampled in the 2008 field season to evaluate the potential presence of an active, locally-controllable source of PCBs, a literature review of potential PCB source areas in the Hamilton Harbour watershed was conducted as recommended following the 2007 field season (Labencki, 2009). Known historical sources of PCBs to the Harbour were documented, along with anomalous PCB concentration results in any media which may suggest a nearby source. All water discharge points to the Harbour were also noted, regardless of historical PCB absence or presence. Water inputs characterized in 2007 were not addressed explicitly in the literature review as results from the 2007 field season suggested that inflows from Woodward Ave and Skyway WWTPs, and the Red Hill, Indian and Grindstone Creeks do not represent large, locally-controllable sources of PCBs to Hamilton Harbour (Labencki, 2009). a) Potential PCB Sources Integrated at the Windermere Arm-Windermere Basin Bridge

There are a number of potential PCB sources in the very southeast corner of the Harbour that are integrated at the Windermere Arm-Windermere Basin Bridge before being discharged to Windermere Arm. The Woodward Ave WWTP is a potential PCB source, although its flows were characterized during the 2007 sampling and absolute PCB concentrations were found at levels that do not support this WWTP being a large PCB source to the Harbour; the PCB congener pattern also did not support the WWTP being the major source of PCBs to Windermere Arm (Labencki, 2009). It remains on the potential PCB source list however as PCB concentrations measured in 2007 were highly variable indicating that concentration spikes at the plant may occur; the magnitude and duration remain unknown.

Another potential PCB source area discharging to Windermere Arm via the Windermere Arm-Windermere Basin Bridge are the lands adjacent to the lower portions of the Red Hill Creek and Windermere Basin (north of Brampton Street) as these areas



were not encapsulated in the 2007 sampling campaign (except for effluent from the Woodward Avenue WWTP, which does not appear to be a major PCB source). Harlow and Hodson (1988) identified the lands adjacent to Windermere Basin as a potential source area:

….the most important additions of PCBs seem to be from an unknown source to Windermere Basin and storm sewers draining an industrial property where transformers were once manufactured. Hence, high levels of PCBs have been measured in the water (up to 90 ug/L) and sediments in the Basin and near the Strathearne Slip (Harlow and Hodson, 1988, p. 72).

Consistent with Harlow and Hodson’s (1988) identification of Windermere Basin

as a receptor of high PCB loadings, is the historically high PCB concentrations in Windermere Basin sediment. In MOE (1985), the total PCB surface sediment concentration for 1975-1980 at the inflow to Windermere Arm ranged from 200,000 – 1,800,000 ng/g dw and in the Windermere Basin, a value of 10,000,000 ng/g dw was measured (MOE, 1985, p.71). As it is not clear what source(s) contributed to these high levels in sediment or if the source no longer contributes PCB loadings, the Windermere Basin area remains as a potential PCB source area. One possible source to the Windermere Basin is the Parkdale CSO, which discharges directly to the Basin on the south side and has been identified by the HH RAP as a historical contamination source.

In addition to Windermere Basin, the lower Red Hill Creek remains as a potential PCB source area. The Rennie and Brampton Street landfills were known historical sources of PCBs to the Red Hill Creek, however, these sites are likely no longer of significant concern due to recent clean-up activities at the closed landfill sites. In 2003 (Rennie) and 2004 (Brampton), a leachate collection system came online in the area surrounding the closed landfill sites to mitigate contaminated groundwater from entering Red Hill Creek. Preliminary monitoring results from Red Hill Creek and leachate collection system suggested that the system appeared to be functioning as intended through mitigating the migration of impacted groundwater to the Creek (City of Hamilton Public Works Department, 2008). b) Potential PCB Sources Integrated in the Strathearne Avenue Slip

The Strathearne Avenue Slip integrates a few potential PCB sources to the Harbour, of particular note being the Strathearne Ave CSO which discharges to the southwest corner of the Slip. As identified in reports from the 1980s, the Strathearne Avenue CSO was a known source of PCBs to the Harbour. Following some investigative work completed in the early 1980s, MOE (1985) states that:

PCB’s were consistently found at the Strathearne St. outfall, a previous transformer manufacturing site, at concentrations of 0.46



to 5.3 ug/L and as high as 180 ug/L in oil residues (MOE unpublished data). These data are in accord with finding the highest sediment PCB concentrations in the southeast part of the harbour (MOE, 1985, p. 25)

In addition, Harlow and Hodson (1988) state:

From about 1965 to 1978, a Westinghouse plant in Hamilton made electrical transformers that required Arochlor 1254 and 1260 (polychlorinated biphenyls, PCBs) as thermostable dielectric fluids. This plant was located above the Strathearne sewer but records of amounts used or discharged are not available (Duffus 1986). Continuous PCB emissions from the steel mills are unlikely since MOE has not found PCBs in steel company effluents (Vogt 1986), but periodic spills from electrical equipment may occur (Harlow and Hodson, 1988, p. 28)

and

Leachate from the Westinghouse transformer plant site may have also entered the Strathearne Slip and the south shore zone, an area heavily contaminated with PCBs (MOE 1985; 1986e; also see section 3.6, levels in water and sediment). Since levels in water in the Strathearne Street slip are usually 0.46 – 5.3 ug/L, and occasionally as high as 180 ug/L (MOE 1986e), PCBs may still be leaching from the old Westinghouse site, from its sewers, or from contaminated bottom sediments in the slip (Harlow and Hodson, 1988, p. 32)

Lands within the Strathearne Avenue Slip sewershed are clearly a historical

source of PCBs to the Harbour; however, it is unknown if the Strathearne Avenue CSO or nearby land runoff are present day PCB sources. The only other outfall in the Strathearne Avenue Slip noted in the Canadian Great Lakes Basin Intake-Outfall Atlas is the Ferrous Wire Manufacturing outfall (75% cooling water; 25% water from roof drains) of Stelco Inc. Parkdale Works (Kleintfeldt Consultants Limited, 1990).

Also unknown is the degree to which bottom sediments in the Slip are a present day PCB source, as noted by Harlow and Hodson (1988). Milani and Grapentine (2006a) measured total PCB concentrations of 5,200 ng/g and 1,500 ng/g at two stations in the Slip, the former of which is located further south in the Slip and is approximately four times greater than average PCB concentrations in the surface sediments of Windermere Arm. This station also had an anomalous Aroclor pattern, as it was composed of Aroclors 1242 and 1260, relative to the other station in the Slip and other stations in the Harbour which were composed of Aroclors 1254 and 1260.



Sediment sampling conducted prior to 2007 navigational dredging in the Strathearne Avenue Slip also demonstrated increasing total PCB concentrations towards the south end of the Slip, with a total PCB concentration of 11,000 ng/g (ASI Group, 2006) near where Milani and Grapentine (2006a) reported a concentration of 5,200 ng/g. ASI Group (2006) reported the presence of Aroclors 1242, 1254 and 1260 in the samples, corroborating the unique presence of Aroclor 1242 in the Slip. PCB concentrations in sediment at the south end of the Strathearne Avenue Slip are elevated on a Harbour-wide basis and appear to be variable, and thus have the potential to be a present day PCB source to the Harbour. c) Potential PCB Sources Integrated in the ArcelorMittal Dofasco Boatslip Like the Strathearne Avenue Slip, the ArcelorMittal Dofasco Boatslip also integrates a few potential PCB sources to the Harbour. Either historically or at present, a large PCB source has discharged/is discharging to the ArcelorMittal Dofasco Boatslip as suggested by the present elevated PCB concentrations in surface sediment.

Total PCB concentrations in surface sediment sampled in 1999 were up to 19,000 ng/g at the south end of the Slip (Jaagumagi et al., 2003), an order-of-magnitude greater than the area-averaged 2003 Windermere Arm PCB surface sediment concentration (1,270 ng/g; Labencki, 2008). PCB concentrations in surface sediment generally increased toward the south end of the Slip, with mid-slip stations averaging 7,400 ng/g (Jaagumagi et al., 2003). Another sediment survey conducted in 2000 by Environment Canada corroborated the 1999 MOE survey and found an average total PCB concentration of 6,167 ng/g at mid-Slip (Milani and Grapentine, 2006a); the PCB concentration primarily consisted of Aroclors 1260 and 1254. Milani and Grapentine (2006a) also noted that the highest PCB concentration in surface sediment of 44 stations sampled in Hamilton Harbour were from the ArcelorMittal Dofasco Boatslip station (mid-Slip); PCB concentrations are known to be even higher in the southern end of the Slip (Jaagumagi et al., 2003), emphasizing the relatively high PCB sediment contamination in the Slip on a Harbour-wide basis.

PCB investigations in the ArcelorMittal Dofasco Boatslip have also included deployment of caged mussels in the Slip during the late 1990s (Jaagumagi et al., 2003). PCB concentrations in caged mussel tissue were up to 400 ng/g - an order-of-magnitude higher than PCB concentrations in mussels deployed in locations outside the Slip. As mussels obtain their PCB body burden from PCBs in the water column, caged mussel results suggest elevated PCB concentrations in the water column in the ArcelorMittal Dofasco Boatslip, in addition to previously noted high PCB concentrations in surface sediment.

The source of PCBs to the ArcelorMittal Dofasco Boatslip is unclear, however, a location mid-slip integrates water from a number of potential sources. One potential



source includes the Kenilworth CSO, the outfall of which is located mid-slip on the east side. Other potential sources to the Slip include discharge water from ArcelorMittal Dofasco outfalls1, East Boat slip stormwater sewer (Jaagumagi et al., 2003), and any inputs from contaminated surface sediment. d) Potential PCB Sources Integrated in the Centre of Windermere Arm

There are a number of potential PCB sources in the Windermere Arm area of the Harbour that are integrated in the centre of Windermere Arm. These sources include those detailed above for the Windermere Arm-Windermere Basin Bridge, and the Strathearne Avenue Slip, but additionally, any other uncharacterized sources including outfalls located along the walls of the Arm. For example, the Canadian Great Lakes Basin Intake-Outfall Atlas indicates that the Rod Mill outfall of the Stelco Inc. Parkdale Works, discharges to Windermere Arm, just southeast of station 352 on the southwest wall of the Arm (Kleintfeldt Consutants Limited, 1990). Additionally, the more southern pond located at Pier 22 has hydraulic connections to the Harbour, and could be a potential PCB source given the construction of the north Hamilton industrial lands from fill material. e) Potential PCB Sources Integrated at the Windermere Arm Mouth All of the potential PCB sources discussed in a) to d) above are integrated at the Windermere Arm mouth before being discharged to the main basin of the Harbour. In addition to these potential sources are any uncharacterized sources and the Pier 27 confined disposal facility (CDF), which are all potential PCB contributors to the Windermere Arm mouth location.

At present there is no clear evidence that the CDF contributes PCBs to Hamilton Harbour but is included as part of due diligence in evaluating all potential PCB sources to Hamilton Harbour. The CDF holds navigational dredgate and due to the ubiquitous nature of PCB-contaminated sediment in Hamilton Harbour, the CDF more than likely contains PCB-contaminated sediment. If the CDF contains sediments that were dredged from the Harbour a decade or more ago, these sediments may have a higher PCB content relative to sediment currently present in the Harbour due to observed declining PCB concentrations in surface sediment over time throughout the Harbour (Labencki, 2008). The potential for high PCB concentrations in the CDF is supported by 1 ArclorMittal Dofasco currently has only three active outfalls into the boatslip, and has no active sources of PCBs on the property surrounding the boatslip nor discharging into the three outfalls. An annual Municipal/Industrial Strategy for Abatement (MISA) Report is submitted to the MOE each year which includes data for the three outfalls that discharge directly into the boatslip. ArcelorMittal Dofasco also has low flow non-contact cooling water and clean groundwater flow that goes into the Kenilworth slip just east of the boatslip. -S. Rajkumar (2011, pers. comm.)



data in Holmes (1986) which reported a total PCB concentration in cell 2 of an east Hamilton CDF of 40 ug/L; however, the suspended solids concentration was very high, 26,316 mg/L, equating to a suspended solids PCB concentration of 1.52 ug/g, a concentration similar to that in Windermere Arm surface sediment (Labencki, 2008). This suggests that the high PCB concentration in water in the cell was associated with suspended particles and was likely not anomalous in nature.

A challenge in investigating the CDF as a potential PCB contributor to the Harbour is that the PCB congener signature of water and sediment in the CDF would mirror that of the Harbour, making it difficult to identify any potential PCB contributions from the facility through use of PCB signature anomaly techniques. f) Potential PCB Sources Integrated at the Western end of Hamilton Harbour

A number of potential PCB sources are integrated at the western end of Hamilton Harbour including sources to Grindstone Creek, sources to Desjardins Canal (Cootes Paradise) or other direct inputs to the western end of Hamilton Harbour; potential PCB sources delivered via the Desjardins Canal is discussed separately below in “g) Potential PCB Sources Integrated in Cootes Paradise”. PCB concentrations were monitored by the MOE in Grindstone Creek water and sediment during 2007; for both media, PCB concentrations were relatively low and did not suggest the presence of an anomalous PCB source to Grindstone Creek (Labencki, 2009). In addition, sediment sampling during 2007 by RBG demonstrated low PCB concentrations in Carroll’s Bay (<10 ng/g – 80 ng/g; Bowman and Theysmeyer, 2008) relative to the main basin of Hamilton Harbour (~500 ng/g; Labencki, 2008).

Biomonitoring studies in the Grindstone Creek delta however; have found relatively high PCB concentrations in YOY fish sampled in 20062 (Labencki, 2008) and snapping turtle eggs sampled 2001-2003 (de Solla et al., 2007). However, YOY fish are mobile and snapping turtles are long-lived, mobile, and have a complex diet, so the PCB body burden in these biota may not be representative of just the Grindstone Creek delta and/or current conditions in the delta. These observations as well as the elevated PCB concentrations in water at the Desjardins Canal in 2007 suggest the western end of Hamilton Harbour still requires investigation for potential PCB sources. Other potential PCB sources at the western end of Hamilton Harbour include 2 Elevated PCB concentrations in YOY fish during 2006 were not isolated to the Grindstone Creek sampling location as concentrations were also elevated at the CCIW sampling station. Also, it was noted by field staff that the fish sampled from Grindstone Creek in 2006 were relatively large, meaning that the fish were likely yearlings rather than true YOY fish, and may have had a longer period of exposure, hence explaining elevated PCB concentrations in fish tissue (Labencki, 2008).



stormwater runoff and combined sewer overflows (CSOs) such as the Bayfront Park CSO, which has had a storage tank since 1993. The only local outfall for this area of the Harbour noted in the Canadian Great Lakes Basin Intake-Outfall Atlas is the Bar Mill outfall for Stelco Inc., which discharges in the Bayfront Park area (Kleintfeldt Consultants Limited, 1990). g) Potential PCB Sources Integrated in Cootes Paradise

The investigation of potential PCB sources to Cootes Paradise is warranted given the higher than expected PCB concentrations measured in the waters of the Desjardins Canal in 2007 (2.1 – 5.7 ng/L; Figure 2; Labencki, 2009). Although the PCB concentrations were likely reflecting Harbour water quality at this location, more lines-of-evidence are required to evaluate if a potential PCB source exists to Cootes Paradise. Elevated PCB concentrations in snapping turtle eggs were also measured in Cootes Paradise during 2001-2003 (de Solla et al., 2007) suggesting a potential PCB source, although snapping turtles are long-lived, mobile and have a complex diet, so may not be representative of just Cootes Paradise and/or current conditions. A number of potential PCB sources are integrated near the Cootes Paradise outflow at the Desjardins Canal, including sources to Chedoke Creek, sources to Spencer Creek, numerous CSOs, closed landfill sites and the Dundas WWTP. Chedoke Creek is a highly urbanized creek and has been noted by Royal Botanical Gardens (RBG) staff to be the worst quality of water entering Cootes Paradise (J. Bowman, 2008, pers. comm.). The Creek may convey PCBs from various sources, one example being the recently remediated West Hamilton landfill on the eastern bank of Chedoke Creek, as groundwater flow is generally towards the Creek (Gondim and Murdoch, 2009). This site however, along with other closed landfills such as Dundas West and Dundas East (both located in the western end of Cootes Paradise), have been subject to a detailed review and remediation as required (Gondim and Murdoch, 2008). There are also CSOs which discharge to Chedoke Creek, including the Royal CSO, and the Main-King CSO, the latter of which now has a mitigation storage tank. One challenge with evaluating potential PCBs sources to Cootes Paradise from Chedoke Creek by monitoring water quality at a location in Cootes Paradise near the outflow at the Desjardins Canal is “short-circuiting”. Water from Chedoke Creek does not mix well with water in Cootes Paradise, but regularly “short circuits” the marsh and flows along the east shore, then straight out into the Harbour via the Desjardins Canal (J. Bowman, 2008, pers. comm.). Thus, PCB concentrations in water measured at the Desjardins Canal may be reflecting inputs from Chedoke Creek, without evidence of these PCB inputs in Cootes Paradise sediment. Results of sediment sampling in 2006 by RBG indicated low PCB sediment concentrations (<detection – 110 ng/g) in Cootes Paradise (Bowman, 2007). As such, a Cootes Paradise monitoring station intended to integrate all potential incoming PCB sources to the marsh may not fully characterize



inputs from Chedoke Creek, and as such, the Creek should be monitored directly. Other potential PCB sources in Cootes Paradise (excluding sources to Chedoke Creek) are CSOs (Sterling CSO - via Western Inlet; Ewen CSO - via Coldwater Creek), closed landfill sites (as noted previously) and the Dundas WWTP. The Dundas WWTP discharges effluent to the western end of Cootes Paradise and is a potential PCB source to Cootes Paradise, although not highly suspect due to relatively low PCB concentrations measured in Cootes Paradise sediment in 2006 (Bowman, 2007). Nonetheless, if PCBs are being discharged from the Dundas WWTP, they would certainly be present in sludge due to the affinity of PCBs for particles; a relatively low PCB concentration in sludge would suggest relatively low PCB inputs to the WWTP in general. h) Potential PCB Sources Integrated Along the North Shore of Hamilton Harbour

A number of potential PCB sources are integrated along the north shore of Hamilton Harbour including sources to Falcon Creek, sources to stormsewers, a transformer station and any other uncharacterized sources to the north shore of Hamilton Harbour. PCB water concentrations were monitored by the MOE in Indian Creek during 2007 and were found to be relatively low; results did not suggest the presence of an anomalous PCB source to Indian Creek (Labencki, 2009).

Some historical PCB monitoring results for surface sediment suggest a potential PCB source on the Hamilton Harbour north shore. The highest PCB concentration measured during the 1982 surface sediment survey of Hamilton Harbour was 1,270 ng/g3 at station 257 (MOE, 1985; MOE, 1986), located near LaSalle Marina on the north shore. Both MOE (1985) and MOE (1986) note that sediment in the LaSalle Marina area has had historically low concentrations of most pollutants, suggesting that the PCB concentration results for station 257 during 1982 were anomalous. Further, during the same 1982 survey, the PCB concentration of sediment from station 268 (Windermere Arm-Basin Bridge) was below the detection limit, also an anomalous result given that station 268 had the highest PCB concentration (10,100 ng/g) of the 1972 survey (MOE, 1974, p.G3). It is this author’s opinion that the results for stations 257 and 268 may have been transposed for the reporting of the 1982 survey results, as anomalously high surface sediment PCB concentrations along the entire north shore of Hamilton Harbour had not been reported for surveys prior to 1982 (MOE, 1974, p.G6; MOE, 1986, p.5), and have not been reported since (Milani and Grapentine, 2006a). Nonetheless, potential PCB sources to the north shore of Hamilton Harbour are still considered out of due diligence.

3 Wet weight or dry weight was not specified; Harlow and Hodson (1988) cautioned that some older data are reported in ng/g ww.



As noted in the Canadian Great Lakes Basin Intake-Outfall Atlas (Kleintfeldt Consutants Limited, 1990), the only outfalls located along the north shore of the Harbour are stormsewers, which could be a potential PCB source. In addition, Harlow and Hodson (1988) make mention of a potential PCB source somewhere along the Harbour’s north shore in Burlington, which may explain the 1982 sediment survey results, or may be unrelated due to the unknown location of site described; it is described as follows:

On the north shore in Burlington, the Ontario Hydro transformer station may have contributed PCBs through spills on soil that generated leachate. Current practice at the site is to excavate any stone and gravel on which more than 50 mg/kg PCB was spilled and store it in drums. There are about 350 drums of this type on the site (DellaRossa 1986)4. (Harlow and Hodson, 1988, p. 32)

In addition to potential PCB sources, the geography and hydrodynamics of the north shore are also important to consider in PCB investigations. The eastern half of the Harbour’s north shore is a non-depositional area (MOE, 1985, p.79) meaning any incoming PCBs are not expected to accumulate close to their source in this area (i.e. in sediment). Also important to consider are the two main counter-clockwise rotating eddies in the Harbour. The larger counter-clockwise eddy occupies the deeper part of the Harbour with the mid-point in-line with LaSalle Marina in the north (Rao et al., 2009), thus, a location near LaSalle Marina integrates potential PCB sources from the north shore. i) Potential PCB Sources Integrated near Randle Reef/South Shore of Hamilton Harbour

A number of potential PCB sources are integrated at the southern shore of Hamilton Harbour near Randle Reef, including CSOs, stormsewers, industrial outfalls and other uncharacterized sources to the southern shore of Hamilton Harbour.

Historical sediment surveys suggest the potential presence of a PCB source along the southern shore of Hamilton harbour, although contemporary survey results are somewhat unclear. The 1972 surface sediment survey of Hamilton Harbour demonstrated that PCB concentrations at station 262 near Randle Reef (3,000 ng/g) were the second highest after concentrations measured at station 268 at the Windermere Arm-Basin Bridge (10,100 ng/g) (MOE, 1974). The third highest PCB concentration in this survey was measured at station 15 (2,000 ng/g), near the northwest corner of the Centennial Dock near Bayfront Park (MOE, 1974). It is unknown what sources contributed to these elevated PCB concentrations along the south shore of the Harbour.

4 Currently, there is a large transformer station at King Road and highway 403 in Burlington, however, due to a lack of location details in Harlow and Hodson (1988), this may or may not be the transformer station of note on page 32 of Harlow and Hodson (1988).



A more recent survey of the Harbour conducted by NWRI in 2000, indicates high variability in PCB concentrations within surface sediment sampled from the Randle Reef/south shore area of the Harbour. PCB concentrations ranged from 100 ng/g to 1,700 ng/g, and most stations had concentrations similar to those measured in the deeper part of the Harbour, e.g. ~500 ng/g (Milani and Grapentine, 2006a). Overall, the 2000 sediment survey results for the Randle Reef area are somewhat unclear, as:

• The maximum and second highest concentrations of 1,700 ng/g, and 900 ng/g, respectively, measured near Randle Reef are consistent with the PCB concentrations found in PCB-contaminated areas of Windermere Arm, indicating the potential for a current PCB source in the Randle Reef area;

• The PCB concentration of 840 ng/g in the Emerald St slip is slightly higher than background concentrations in the main basin of the Harbour, indicating the potential for a current PCB source to the southern shore of the Harbour;

• The inconsistent nature of PCB concentrations along the southern shore (i.e. high variability in PCB concentrations measured at stations in close proximity) may be reflective of historical contamination and subsequent deposition patterns, rather than inputs from a current PCB source; and

• The lower PCB concentrations measured in 2000 relative to 1974 may be indicative of a reduction in local PCB inputs.

While there may have been a historical PCB source discharging to the southern shore of the Harbour, it may or may not be currently active, and thus potential PCB sources to the area are considered. Potential PCB sources to the south shore of Hamilton Harbour include numerous CSOs (Birch, Wentworth, Wellington, James), at least three storm sewers (Kleintfeldt Consutants Limited, 1990) and any inputs from contaminated surface sediment. In addition, industrial outfalls are also potential sources; outfalls in the southern shore area noted in the Canadian Great Lakes Basin Intake-Outfall Atlas include a cooling water outfall from the Canadian Vegetable Oil facility, and two Basic steel making outfalls from Stelco Inc. (Kleintfeldt Consutants Limited, 1990). Important to note is that runoff water from the old, industrial core of the City of Hamilton flows into the Harbour in the Randle Reef/Sherman Inlet area. j) Potential PCB Sources Integrated in the Ottawa Street Slip

There are CSOs that discharge to the Ottawa Street Slip (Ottawa CSO, Plymouth CSO), as well as other (industrial) outfalls (Kleintfeldt Consutants Limited, 1990). While the Ottawa Street Slip remains a potential PCB source to the Harbour, evidence available suggests that there is not an active PCB source being discharged to this Slip. PCB concentrations measured in sediment in the Ottawa Street Slip in 2000 were 750 ng/g (station 7053) and 870 ng/g (station 7014) (Milani and Grapentine, 2006a), consistent with background PCB concentrations which have been measured in the main basin of the Harbour (Labencki, 2008).



A subsequent survey conducted in 2007 by Environment Canada also did not find evidence of a PCB anomaly in the Ottawa Street Slip. Total PCB concentrations in surface sediment samples collected from the top/head (43.27338, -79.80715), middle (43.27557, -79.80639) and mouth (43.27985, -79.80442) of the Ottawa Street Slip were 49.4 ng/g, 560.6 ng/g and 730.8 ng/g, respectively (D. Burniston and C. Marvin, 2011, pers. comm.). While the middle and mouth locations again have total PCB concentrations consistent with those observed in the main basin of the Harbour, the top/head location has concentrations lower than background (Labencki, 2008). Thus, data suggest that PCB follow-up action in the Ottawa Street Slip is not warranted. k) Other Potential PCB Source Areas

While potential PCB sources to Hamilton Harbour described in a) to j) above would likely be detected though strategically located stations that integrate a given set of sources (as a) to j) are organized above), there are other potential PCB sources to the Harbour that should be mentioned for completeness, including diffuse, non-point sources of PCBs. The presence of such sources are logistically difficult to evaluate, as traditional PCB tracking techniques cannot be used due to no obvious gradients in PCB concentrations between stations. Some of these potential sources may be detected at a number of sampling stations as “background” PCB concentrations. Other potential PCB source areas include: i. Overland flow Overland flow is a potential PCB source and may enter the Harbour at any location. ii. Atmospheric deposition Direct atmospheric deposition of PCBs to the Harbour remains a possibility, albeit an unlikely large source relative to others as it does not explain the spatial pattern of higher PCB concentrations in Windermere Arm. iii. Subsurface/groundwater flow Subsurface or groundwater flow is another potential PCB source in Hamilton Harbour. While PCBs are hydrophobic chemicals and are not readily transported by groundwater due to their tendency to bind to particles in the subsurface, this potential source should not be omitted entirely from consideration. Subsurface or groundwater flow should be considered due to the potential for flow through fractures of the fill material of the south shore, and the history of how the industrial Portlands of Hamilton were constructed. Hamilton Harbour has a long history of dredging activity due to navigational requirements for the busy port. The report written by Holmes (1986) outlines when areas of the Harbour were dredged, and where these sediments (spoils) were placed either as fill material in land reclamation, or alternatively to confined disposal facilities (CDFs):



The present shoreline configuration is the result of extensive wharf construction and land reclamation in the 1950s (west end), the 1960s (east end), and some reconstruction during the 1970s. Stelco and Dofasco also carried out major expansion and land reclamation projects on their properties during the 1950s and 1960s. Most of the wharves were constructed with a perimeter berm of stone or slag and the interior filled with material dredged from the adjacent channels and berths (Grossi 1985). Dredging activity peaked between 1957 and 1960 when the approach channel, turning basin, and slip to the Strathearne Avenue wharves (Piers 23 and 24) were dredged. Although most of the sediments were used in land reclamation during this period, an unspecified quantity was dumped into the deeper waters of the harbour at an unknown location. (Holmes, 1986, p.94).

In addition:

The development of the CDF was initiated in 1958 when a portion of the material dredged from the Strathearne Avenue wharves was placed in the Pier 25 location (Grossi 1985). DPW records indicate major berm construction occurred in 1958, 1966, and 1972. (Holmes, 1986, p.97)

While contaminant concentrations in sediment are not part of the discussion in Holmes (1986) on the history of dredging and land reclamation in Hamilton Harbour, implications of historical dredging practices can be inferred. PCBs were in heavy use during the 1950s and 1960s, the same time period that sediments were being dredged from the Windermere Arm area of Hamilton Harbour and being used for land reclamation in other parts of the Harbour. This leaves the possibility that PCB-contaminated sediments may form part of the land mass of the Harbour portlands, including the land at piers 25, 26 and 27, which were built on CDFs. While the spoils used in land reclamation were likely contaminated to some extent, contaminant transport via flow from these areas to the Harbour has not been demonstrated to date. l) Recommended Sampling Stations

The recommended sampling stations to investigate the potential presence of any active, locally-controllable sources of PCBs, were selected to integrate potential PCB source areas; these recommended stations are as follows: • Station 268 (Windermere Arm/Basin bridge) – Integrates inputs from: Woodward

Ave WWTP, Red Hill Creek (including potential inputs from Rennie and Brampton Street landfill sites), Parkdale CSO, and unknown sources to Windermere Basin;

• Station 258 (Hamilton Harbour centre station) – Hamilton Harbour “reference” station;

• Station 352 (mid-Windermere Arm) – Integrates inputs from: upstream stations (268, 366), outfalls along walls of Windermere Arm, Pier 22 pond; Windermere Arm



“reference” station; • Station 365 (Adjacent to Randle Reef) – Integrates inputs from: south shore CSOs,

stormsewers, industrial outfalls, any inputs/resuspension from contaminated surface sediment (i.e. Randle Reef), unknown sources to south shore.

• Station 366 (Strathearne Street slip - south end) – Integrates inputs from: Strathearne CSO, industrial outfall, and any inputs/resuspension of contaminated surface sediment;

• Station 367 (West end of Hamilton Harbour near Desjardins Canal) – Integrates inputs from: Grindstone Creek, Desjardins Canal (Cootes Paradise), stormwater, CSOs (Bayfront Park), industrial outfall, unknown sources to west end of Harbour;

• Station 368 (North end of Harbour near LaSalle marina) – Integrates inputs from: Falcon Creek, stormsewers, transformer station, unknown sources to north shore;

• Station 369 (ArcelorMittal Dofasco boat slip - mid-slip) – Integrates inputs from: Kenilworth CSO, industrial outfalls, inputs/resuspension of contaminated surface sediment;

• Station 370 (Mouth of Windermere Arm – northwest corner of Pier 27 confined disposal facility (CDF) – Integrates inputs from: upstream stations (268, 366, 369, 352) and Pier 27 CDF.

• Station 371 (Cootes Paradise) – Integrates inputs from: Chedoke Creek, Spencer Creek, CSOs, closed landfill sites, Dundas WWTP

1.1.2 Resuspension of PCB-Contaminated Sediment

Following the finding that PCB concentrations in the Harbour were on par with or greater than PCB concentrations in Harbour inflows during 2007, a recommendation was also made to follow-up on whether resuspension of PCB-contaminated sediment is a primary driver behind elevated PCB water concentrations in Hamilton Harbour. This recommendation was worded as follows in the HH RAP report summarizing the 2007 field season in Hamilton Harbour:

Follow-up field work and sampling should also be conducted to determine if resuspension of PCB-contaminated sediment is a primary driver behind elevated PCB water concentrations in Hamilton Harbour. In order to assist with such an investigation, it is recommended that at stations sampled in the Harbour-wide investigation for Recommendation #3, that paired water samples be collected from both the top of the water column, and near the sediment bed; these samples should be analyzed for both PCBs and TSS. Comparison of these paired samples at each station should reveal if PCB concentrations are correlated to TSS concentrations and if there is a PCB concentration gradient from the sediment bed towards the surface as a result of resuspension of PCB contaminated surface sediment. Additionally, measurement of the proportion



PCBs in the dissolved-phase relative to the particle-phase in Harbour water samples should also assist in this investigation, as well as the investigation noted in Recommendation #3. (Labencki, 2009, p.88).

Follow-up actions to this recommendation were pursued in the 2008 field season

with a focus on Windermere Arm and the boat slips due to known elevated levels of PCBs in sediment (see 1.1.1 Determination of an active, locally-controllable source of PCBs; also, Labencki, 2008; Milani and Grapentine, 2006a; ASI Group Ltd., 2006; Jaagumagi et al., 2003), the elevated levels of PCBs in water relative to main basin of the Harbour (Figure 2) and the potential for Harbour-wide recirculation of historically-contaminated sediments from this potential source area.

The 2008 field work related to resuspension was conducted in conjunction with the investigation into the potential for an active PCB source. During stratification, the impact of any external PCB sources on measured concentrations in the Harbour would be higher in the epilimnion as inflows are generally discharged to this portion of the water column. In theory, a higher PCB concentration at the sediment bed relative to the surface suggests the potential for resuspension. Additionally, the measurement of paired PCB and TSS samples during the 2008 field season is an important aspect of determining the relationship between these parameters and whether resuspended PCBs from surface sediments are a likely source of PCBs in the water column. Ideally, monitoring of PCBs in the dissolved versus particulate phase should also be conducted to determine the role of particles in ambient PCB concentrations, however, the MOE analytical method for PCBs is based on whole water samples. Ambient PCB concentrations analyzed separately for the dissolved and particulate phases are available however from Environment Canada who sampled 10 Harbour stations between April and November 2008. If resuspension is a major driver in the Harbour, then major changes in PCB whole-water concentrations could be correlated to PCBs in the particle-phase.

Also to be considered is the PCB concentration of the suspended sediments (i.e. ng PCB/g sediment). Knowing that resuspension is a major driving force will assist the Hamilton Harbour RAP in explaining why PCB concentrations in surface sediment have not been decreasing in recent years, and following this, why PCBs in sport fish are also not declining to acceptable levels. This information is vital in managing expectations for the BUI Restrictions on Fish and Wildlife Consumption. What is driving the PCB concentrations observed in the Harbour and fate/transport processes need to be understood for remedial actions to ultimately be developed and delisting to be achieved.



1.1.3 Follow-up to determine source of PCBs measured at the Desjardins Canal

Following the finding of elevated PCB concentrations in water at the Desjardins Canal during 2007, a recommendation was made to follow-up on whether PCB concentrations at the Desjardins Canal were reflective of water from the Harbour, or an uncharacterized PCB source to Cootes Paradise. This recommendation was worded as follows in the HH RAP report summarizing the 2007 field season in Hamilton Harbour:

Follow-up field work and sampling should be conducted to determine if elevated PCB concentrations measured at the Desjardins Canal during 2007 represent flow from Hamilton Harbour, or an uncharacterized PCB source to Cootes Paradise. Although lines-of-evidence suggest that the water at the Desjardins Canal is likely from the Harbour (e.g. total PCB concentrations at the Canal are similar to Hamilton Harbour centre station, PCB congener profiles are similar between the Canal and Hamilton Harbour centre station), due diligence should be employed given the sensitive nature of Cootes Paradise, and the full Harbour-wide PCB investigation recommended above (Recommendation #3). This recommended local-scale PCB investigation into the potential presence of an active PCB source to Cootes Paradise should focus on eliminating potential PCB sources such as the Dundas WWTP, Spencer Creek and Chedoke Creek. A combination of media should be used in the investigation, such as grab water samples, SPMDs, and sludge samples from the WWTP. PCB concentrations in sludge samples collected from the Dundas, Woodward Ave and Skyway WWTPs could be compared to determine the relative presence of PCBs in each of the respective sewersheds; thus, the potential magnitude of PCB in effluent from the Dundas WWTP could be extrapolated given the known levels from the Woodward Ave and Skyway WWTPs measured during 2007. (Labencki, 2009, p.88).

Follow-up actions to this recommendation were pursued in the 2008 field season through sludge sampling at the WWTPs, water sampling in Chedoke Creek and placement of an SPMD in Cootes Paradise, as per the selection of stations in the Harbour following the literature review in 1.1.1.1 Literature Review of Potential PCB Sources in the Hamilton Harbour Watershed.

1.1.4 Follow-up to determine recent PCB exposure by YOY fish

PCB concentrations in young-of-the-year (YOY) fish sampled in 2006 from the Grindstone Creek delta and adjacent to the Canada Centre for Inland Waters (CCIW) were elevated relative to previous years (Labencki, 2008). As such, a recommendation



was made to follow-up on whether local PCB exposure had recently increased by sampling YOY fish again during the 2007 season. However, sampling of YOY fish in 2007 was forfeited as not enough fish were located to form a sample (Labencki, 2009). Following this, a recommendation was made to re-attempt YOY fish sampling in 2008. This recommendation was worded as follows in the HH RAP report summarizing the 2007 field season in Hamilton Harbour:

YOY fish sampling should be re-attempted at the locations sampled in 2006 (Grindstone Creek, CCIW) to determine if elevated PCB YOY fish concentrations observed in 2006 represent an increasing trend in PCB exposure in Hamilton Harbour (Labencki, 2009, p.88).

Follow-up actions to this recommendation were pursued in the 2008 field season.

1.2 2008 Field Season Objectives The primary objective of the 2008 field season sampling was to follow-up on the recommendations made following the 2007 field season, particularly to determine the cause of elevated PCB concentrations in Hamilton Harbour (e.g. active PCB source, or internal PCB cycling/resuspension). Data that were gathered in 2008 were collected to answer the following specific questions: 1) Are there any active, locally controllable PCB sources to Hamilton Harbour? 2) Can internal PCB cycling/resuspension from historically-contaminated sediment

explain the high PCB concentrations in Hamilton Harbour water and sediment? 3) How does fate and transport of PCBs in Hamilton Harbour play into the PCB

concentrations observed in the local foodweb? 4) Are there any remedial and/or management actions possible to address the BUI

Restrictions on Fish and Wildlife Consumption? 5) Has PCB exposure increased in recent years? Data collected in 2008 were also intended to help determine the role PCB fate and transport processes play in the BUI restrictions on fish and wildlife consumption. Results are intended to be used by the Hamilton Harbour RAP Toxic Substances and Sediment Technical Team to make educated decisions on what management or remedial action(s) (if any) is/are required to address the BUI Restrictions on Fish and Wildlife Consumption. More specifically, following analysis of the 2008 data, it is anticipated that a decision can be made on whether an active source, resuspension or both are driving the pertinent BUI. Thus, the 2008 field work also acts to help close the loop on whether there is an ongoing, locally-controllable active source of PCBs to the Harbour, an action recommended in numerous reports (Harlow and Hodson, 1988; HH



RAP, 1992; HH RAP, 1998) and formed the basis of the 2007 field season (Labencki, 2009).

Currently, the Hamilton Harbour RAP is aiming to delist in 2015 which currently requires that there be no restrictions on the consumption of fish from the harbour attributable to local sources (HH RAP, 2003). Greater understanding of the fate and transport of PCBs in Hamilton Harbour is necessary before a definitive management action (if any) can be implemented.

1.3 2008 Field Season Limitations

Limitations of the 2008 field season sampling and data analysis were identified a priori; these project limitations were acknowledged to assist with data interpretation and included the following: • As shown in the 2007 sampling campaign results, PCB concentrations can be highly

variable in water, which may influence the determination of what process(es) is/are driving PCB concentrations in sport fish. There are a number of factors that can influence observed PCB concentrations in discrete samples, all of which cannot be known at a given time.

• Processes that are dominant in one season (i.e. summer 2008), may not have been dominant in the past or will be dominant in the future, pending the drivers. Balance needs to be struck between how representative one season may be, versus, the need to move forward. Additional time will likely be required for Harbour recovery if an active PCB source is found, thus lack of absolute scientific-certainty should not cause delay in undertaking reasonable mitigating follow-up actions (i.e. precautionary principle)

• Determination of an active source may be somewhat dependent on rain events to flush contaminants into the harbour and cause a measurable concentration “spike”. Weather cannot be controlled.

• Placement of SPMDs in the harbour may default to the best logistical location as opposed to the best scientific/experiment location.

• Ship traffic is unpredictable, and can impact the planning 2008 sampling activities in Hamilton Harbour through destroying SPMD deployment floats, and causing short-term high resuspension rates. The timing and size of the last ship to pass through a particular area will not be known.

• With no known outfalls to evaluate the potential for a locally-controllable active PCB source in the western end of Hamilton Harbour, choosing a meaningful location to sample is challenging.

• EMRB field crews attempted to re-sample YOY fish in September 2007 at the Grindstone Creek and CCIW locations, however, no fish were found at Grindstone



Creek and only limited numbers were from CCIW. Similar challenges may again be met in the 2008 field season.

• If an active, locally-controllable PCB source is found, appropriate remedial action can be taken to reduce PCBs entering Hamilton Harbour. It must be re-iterated however, that the RAP is only intended to address local issues. If issues driving the pertinent BUI are found to be regional, provincial or federal in nature, then the issues cannot be resolved exclusively by the RAP as RAPs were never intended to address regulatory changes however necessary it may be to address the pertinent BUIs.



2. Methods

2.1 Water sampling in Hamilton Harbour

Five water sampling surveys were conducted during the 2008 field season in Hamilton Harbour (May 28, June 3, June 30, August 19, September 18). During each survey, nine stations were sampled in the Harbour (Table 1; Figure 3); water sampling stations were selected to integrate potential PCB source areas as discussed in 1.1.1.1 Literature Review of Potential PCB Sources in the Hamilton Harbour Watershed. A tenth water sampling station in mid-Strathearne Ave slip (station 372) was sampled on May 28, 2008 in error. Except for the first survey (May 28, 2008) conducted from the MOE’s Kemp Boat, water sampling surveys were conducted from the MOE’s Great Lakes Guardian and these four surveys were timed to coincide with the timing of deployment and retrieval of two separate 28-day deployments of semi-permeable membrane devices (SPMDs) in Hamilton Harbour. A full listing of weather conditions for the 2008 field season is included in Appendix I: May – September 2008 weather conditions in Hamilton. Table 1: Water sampling locations for 2008 field season in Hamilton Harbour.

Station Description Station Code1

Latitude Longitude Water depth

(m) Hamilton Harbour centre station

0258 43° 17’ 19.72” N 79° 50’ 10.5” W 23.5

Windermere Arm/Basin bridge

0268 43° 16’ 8.00” N 79° 46’ 57” W 8.5

Mid-Windermere Arm 0352 43° 16’ 23.92” N 79° 47’ 20.51” W 10 Adjacent to Randle Reef 0365 43° 16’ 37.88” N 79° 50’ 27.82” W 15 Strathearne Ave Slip – south end

0366 43° 15’ 47.3” N 79° 47’ 19.9” W 9.7

West end of Hamilton Harbour near Desjardins Canal

0367 43° 16’ 41.4” N 79° 53’ 9.7” W 5.4

North end of Hamilton Harbour near LaSalle Marina

0368 43° 18’ 9.5” N 79° 50’ 11.5” W 9.7

ArcelorMittal Dofasco Boat slip – mid-slip

0369 43° 16’ 14.0” N 79° 47’ 57.5” W 7.5

Mouth of Windermere Arm – northwest corner of Pier

0370 43° 17’ 2.9” N 79° 47’ 43.1” W 11.2



27 confined disposal facility (CDF) Strathearne Ave Slip – mid-slip

0372 43° 15.0’ 58.2” N 79° 47.0’ 15” W 9.4

1 – all stations prefixed by 09 01

Figure 3: Map of water sampling locations for 2008 field season in Hamilton Harbour

During each survey, two water samples were collected at each station: 1) a depth-integrated water sample (sample type 12; matrix WS); and 2) a grab water sample collected 1 m from the sediment bed (sample type 11; matrix WS). A temperature/conductivity/turbidity/dissolved oxygen (DO) depth profile was also conducted with a water quality sonde (YSI 6920 or AMT 14 or 15) during each survey at each station to determine the presence or absence of a thermocline. If a thermocline was present on the survey date, the depth-integrated water sample was integrated across the epilimnion (epilimnetic-integrated water sample); otherwise, the depth-integrated water sample was integrated across the whole water column from surface to just above the sediment bed5. All depth-integrated water samples (sample type 12) 5 On a limited number of occasions, the depth-integrated sample (sample type 12) was collected from the surface to a depth equal to two times the Secchi disc depth at the station.



were collected with a glug-glug water sampler (Figure 4), and all grab water samples (sample type 11) were collected with a beta bottle (Figure 4).

Figure 4: Instrumentation used to collect water samples during 2008 field season in Hamilton Harbour: depth-integrated samples were collected with a glug-glug water sampler (left) and grab water samples were collected with a beta bottle (right). Note: The photograph on the right was taken August 19, 2008 at Station 367; water in the beta bottle is extremely turbid. New sample bottles were used at each station. Two 1L amber bottles (“3P”) were used to submit water samples for PCB analysis, and one 500 mL PET bottle was used for submission of TSS water samples. All sample containers were rinsed twice, and the second rinse of the 1 L amber bottles (used for PCB analysis) was used to rinse and fill the PET bottles for TSS analysis. All water samples were kept on ice and submitted to the MOE Laboratory Services Branch in Etobicoke, Ontario for analysis of 82 PCB congeners and total suspended solids (TSS). Laboratory methods used for analysis of PCBs and TSS were MOE methods PCBC3459 and SS3188, respectively (Appendix II: MOE Analytical Methods). Quality assurance/quality control (QA/QC) procedures for the water sampling included collection of field blanks, sample replicates and a glug-glug/beta bottle comparison. One field blank (sample type 015; matrix WS) was conducted during each survey, except for June 30 (Table 2). Water for field blanks was filled in the lab with distilled, de-ionized water prior to the field sampling. Once on a randomly selected station, the field blank bottle was opened for the duration of the sampling time on station. Field blanks were analyzed for PCBs only (no TSS analysis).



Table 2: Station locations of QA/QC samples collected during the 2008 field season in Hamilton Harbour Survey Date Field Blank Sample Replicates Glug-glug/beta

bottle comparison May 28, 2008 367 268 Not collected June 3, 2008 352 367 352 June 30, 2008 Not collected 352 367 August 19, 2008 365 367 368 September 18, 2008 258 366 268

Two discrete, replicate whole water samples of both sample types (sample type 11 and 12; matrix WS) were collected from a randomly selected station during each survey (Table 2). Replicates were collected to integrate impacts of field and laboratory variability, and were analyzed for both PCBs and TSS. A comparison between samples collected with a glug-glug versus a beta bottle was conducted to evaluate any sampling artefacts or bias from using a different method to collect depth-integrated samples (glug-glug sampler) relative to bottom grab samples (beta bottle). These QA/QC samples were also collected to evaluate any bias from use of an acrylic beta bottle for sampling PCBs. The glug-glug/beta bottle comparison samples were collected at one randomly selected station per survey where one grab water sample (sample type 11) was collected at 0.5 m depth with a glug-glug sampler while one grab water sample (sample type 11) was simultaneously collected at 0.5 m depth with a beta bottle. The glug-glug/beta bottle comparison samples were analyzed for PCBs only (no TSS analysis).

2.2 Semi-permeable membrane device (SPMD) deployment in Hamilton Harbour

Semi-permeable membrane devices (SPMDs; Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods) were deployed for two discrete 28-day periods in Hamilton Harbour during the 2008 field season. During each 28-day period, SPMDs were deployed at nine stations in Hamilton Harbour and one station in Cootes Paradise (Table 3; Figure 5). The first 28-day deployment period was from June 4 – July 2, 2008; and the second 28-day deployment period was from August 20 – September 17, 2008, except for station 371 which had deployment periods of June 5 – July 3, 2008 and August 21 – September 18, 2008. Two discrete SPMD deployment periods were conducted due to high variability of PCB concentrations in the water column observed in 2007 (Labencki, 2009) and also to examine the role of different temperature regimes on results; for this reason, the two deployment periods were not



consecutive during the 2008 season. Water sampling surveys were conducted at the SPMD stations (Table 1) to coincide with the timing of deployment and retrieval of the two SPMDs deployment periods. A full listing of weather conditions for the 2008 field season is included in Appendix I: May – September 2008 weather conditions in Hamilton. Table 3: SPMD deployment locations for 2008 field season in Hamilton Harbour.

Station Description Station Code1

Latitude Longitude Water depth

(m) Hamilton Harbour centre station

0258 43° 17’ 19.72” N 79° 50’ 10.5” W 23.5

Windermere Arm/Basin bridge

0268 43° 16’ 8.00” N 79° 46’ 57” W 8.5

Mid-Windermere Arm 0352 43° 16’ 23.92” N 79° 47’ 20.51” W 10 Adjacent to Randle Reef 0365 43° 16’ 37.88” N 79° 50’ 27.82” W 15 Strathearne Ave Slip – south end

0366 43° 15’ 47.3” N 79° 47’ 19.9” W 9.7

West end of Hamilton Harbour near Desjardins Canal

0367 43° 16’ 41.4” N 79° 53’ 9.7” W 5.4

North end of Hamilton Harbour near LaSalle Marina

0368 43° 18’ 9.5” N 79° 50’ 11.5” W 9.7

ArcelorMittal Dofasco Boat slip – mid-slip

0369 43° 16’ 14.0” N 79° 47’ 57.5” W 7.5

Mouth of Windermere Arm – northwest corner of Pier 27 confined disposal facility (CDF)

0370 43° 17’ 2.9” N 79° 47’ 43.1” W 11.2

Cootes Paradise (RBG station CP-1)

0371 43° 16’ 46.5” N 79° 53’ 46.8” W 1.2

1 – all stations prefixed by 09 01



Figure 5: SPMD deployment locations for 2008 field season in Hamilton Harbour

SPMD deployment stations were selected to integrate potential PCB source areas as discussed in 1.1.1.1 Literature Review of Potential PCB Sources in the Hamilton Harbour Watershed. Station 371 in Cootes Paradise was also selected based on historical sampling by Royal Botanical Gardens (RBG) at their station CP-1. This station is believed to be a location where Hamilton Harbour waters would have minimal influence, as it is thought that the backflow of Harbour water doesn’t reach CP-1 on a daily basis (J. Bowman, 2008, pers. comm.). Also, CP-1 was believed to be a location where the SPMDs would be unlikely to go dry throughout the summer season as they must remain submerged under water during the full 28-day deployment period; the depth at this station ranges seasonally from 0.75 m to 1.4 m (J. Bowman, 2008, pers. comm.). Station 371 did not have water quality samples collected as water quality samples were collected from Chedoke Creek (2.4 Event-based water sampling in Chedoke Creek) and sludge samples were collected from the Dundas WWTP (2.3 Waste water treatment plant (WWTP) primary sludge sampling). During each deployment period, three SPMDs were deployed per station; SPMD replication was conducted for QA/QC purposes. The three SPMDs per station were wired to the inside of a metal shroud (Figure 6) with care taken to keep SPMDs from touching deployment material and field staff; clean nitrile gloves were worn by field staff during each station SPMD deployment and retrieval. A continuous temperature logger



(“Tidbit”) programmed at 1 hour logging intervals was fastened to the top of each shroud. Metal shrouds encasing the SPMDs were deployed at approximately 3 m depth at each station where depth allowed (Table 4), and shrouds were weighted to the Harbour bottom with steel, and kept buoyant in the water column with a Viny float; the full SPMD assembly is shown in Figure 7.

Figure 6: Photograph of SPMDs being wired to the inside of a metal shroud used to house the SPMDs at each station. Also shown is the Viny float (orange sphere) used to keep the SPMD assembly buoyant in the water column. Table 4: Depth of SPMD deployment (m below surface) at each station during each 2008 deployment period Station Deployment Period 1

June 4 – July 2, 2008 Deployment Period 2 Aug. 20 – Sep. 17, 2008

0258 3.6 – 4.3 2.2 – 2.9 0268 0.5 – 1.5 1 - 2 0352 3.5 – 4.7 3.6 – 4.3 0365 3.5 – 4.2 3.6 – 4.3 0366 2 - 3 2 - 3



0367 3.5 – 4.2 3.5 – 4.2 0368 3.6 – 4.3 3.5 – 4.2 0369 2.0 1 - 2 0370 3.5 – 4.2 3.3 – 4.0 0371* 0.5 0.5 Notes: range indicates the depth of the top and the bottom of the metal shroud in the water column. *Deployment period 1: June 5 – July 3, 2008; Deployment period 2: August 21 – September 18, 2008

Figure 7: General installation set-up of SPMDs in the water column (Figure created by Wendy Page, Great Lakes Unit).

Exceptions to the general SPMD deployment (Figure 7) were set-ups employed at stations 268, 366, 369, and 371. At station 268, the metal shroud was suspended from the Windermere Basin/Arm bridge and weighted down with steel. At station 366, the metal shroud was suspended from the dock wall at the very south end of the Strathearne Ave slip and weighted down with steel. At station 369, the metal shroud was suspended from a signpost in the ArcelorMittal Dofasco boat slip and weighted down with steel. The SPMD deployment at station 371 was different again as due to



the shallow depth, the metal shroud was deployed horizontally instead of vertically in the water column, with steel on the sediment bed to keep the shroud on station and a surface float to keep the shroud buoyant (Figure 8).

Figure 8: Installation set-up of SPMDs at station 371 in Cootes Paradise

The rigged steel, cables, SPMDs in metal shroud, tidbits and viny floats were placed on station using the winch on the MOE’s Great Lakes Guardian, except for station 268 which was deployed from land, and station 371 which was placed overboard on station by hand while on the RBG vessel “Little John”. Upon retrieval, all SPMDs were kept on dry ice and submitted to the Metcalfe lab at Trent University in Peterborough, Ontario for analysis of 33 PCB congeners. Laboratory methods used for analysis of PCBs are described in Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods. Results are expressed as ng PCB/mL triolein or ng PCB/SPMD, which are interchangeable units. QA/QC procedures for the SPMD deployment included triplicate SPMDs deployed per station per deployment period (described above), and the use of SPMD field blanks. SPMD field blanks were identical to sample SPMDs, but were not deployed under water and were used to control for PCB contamination which might arise from exposure to air during deployment and retrieval, and any other contamination from SPMD preparation through to final analysis. Field blanks were removed from storage containers (pre-cleaned glass jars) and exposed to air for the period of time that actual SPMD samples were exposed to air during deployment and retrieval. One field blank SPMD was conducted at each station per deployment period, for a total of 10 field blanks per deployment period. Between deployment and retrievals, field blanks were



stored frozen (-20° C) in the MOE freezers; after retrievals, field blanks were submitted with sample SPMDs on dry ice to the Metcalfe lab for analysis.

2.3 Waste water treatment plant (WWTP) primary sludge sampling Waste water treatment plant (WWTP) sludge was sampled on two discrete occasions during the 2008 field season in Hamilton Harbour – on June 26 and September 4, 2008. On each occasion, sludge from three WWTPs were sampled – the Dundas WWTP, Woodward Ave WWTP and Skyway WWTP (Table 5; Figure 9). Table 5: Primary sludge sampling locations for 2008 field season in Hamilton Harbour Station Description Station Code Latitude Longitude Dundas WWTP A & B composite sludge station

09 03 0003 43° 16’ 4.7” N 79° 56’ 36.1” W

Woodward WWTP north & south sludge composite station

09 03 0004 43° 15’ 5.4” N 79° 46’ 25.1” W

Skyway WWTP 4 tank sludge composite station

09 03 0005 43° 18’ 39.9” N 79° 48’ 5.1” W

Figure 9: Sludge sampling locations for the 2008 field season in Hamilton Harbour.



At each WWTP, primary sludge composite samples (sample type 55, matrix SL) were collected where site-specific sampling ports allowed access to the waste stream. At the Dundas WWTP, composite samples were taken from two primary tanks (“A” and “B”) and homogenized and decanted into sample containers. At the Woodward Ave WWTP, composite samples were taken from two primary tanks (“north” and “south”); samples were initially collected in a non-hexaned on-site stainless steel bucket. Sludge samples collected at the Skyway WWTP were composite samples taken from each of the four primary tanks, and were homogenized and decanted into sample containers. Two 250 mL amber glass jars were used to submit each sludge sample for PCB analysis. All sludge samples were submitted to the MOE Laboratory Services Branch in Etobicoke, Ontario for analysis of total PCBs. The laboratory method used for analysis of PCBs was MOE method PCBT 3270.

2.4 Event-based water sampling in Chedoke Creek Three event-based water samples (two wet, one dry) were collected from Chedoke Creek during the 2008 field season. The two wet samples were collected on May 8, 2008 (following 9.2 mm rain on May 7) and June 16, 2008 (following 25 mm of rain on June 15), and the dry sample was collected on August 26, 2008 (no rain previous 24 hours). Samples were collected from station 09 15 0010 (43° 16’ 7.3” N 79° 53’ 36.1” W) off of the Macklin Street Tunnel Bridge (Figure 10). A full listing of weather conditions for the 2008 field season is included in Appendix I: May – September 2008 weather conditions in Hamilton.

Figure 10: Water sampling location in Chedoke Creek for 2008 field season.



During each sampling event, one grab water sample (sample type 11; matrix WS) was collected mid-depth with a glug-glug sampler. Water depth was confirmed by lead-line to determine sample depth; sample depth was approximately 1.4 m. Two 1L amber bottles (“3P”) were used to submit water samples for PCB analysis, and one 500 mL PET bottle was used for submission of TSS water samples. All sample containers were rinsed twice, and the second rinse of the 1 L amber bottles (use for PCB analysis) was used to rinse and fill the PET bottles for TSS analysis. All water samples were kept on ice and submitted to the MOE Laboratory Services Branch in Etobicoke, Ontario for analysis of 82 PCB congeners and total suspended solids (TSS). Laboratory methods used for analysis of PCBs and TSS were MOE methods PCBC3459 and SS3188, respectively (Appendix II: MOE Analytical Methods).

2.5 Sediment sampling in Strathearne Avenue Slip

An opportunistic (unplanned) surface sediment grab sample (matrix SE) was collected at station 09 01 0366 (Table 1; Figure 3) at the southern end of the Strathearne Avenue Slip on August 19, 2008. The sample was collected due to consistent observations of oil sheens in the vicinity of this station during the 2008 monitoring season. The sediment sample was collected with a ponar sampler and was a single grab sample (sample type 51; matrix SE) from the surface to approximately 3 cm depth. The sediment sample was homogenized with a stainless steel spoon in the field (Figure 11) and submitted to the MOE Laboratory Services Branch in Etobicoke, Ontario for analysis of PCB congeners (55 congeners), PAH compounds (18 compounds) and total organic carbon (TOC). Laboratory methods used for analysis of PCBs, PAHs and TOC were MOE methods PCBC3412, PAH3425 and ORGC3012, respectively (Appendix II: MOE Analytical Methods).



Figure 11: Sediment sampled August 19, 2008 from station 366 in the Strathearne Avenue slip.

2.6 Young-of-the-year (YOY) fish sampling In response to elevated PCB results in 2006 and recommendations in the 2007 monitoring report (Labencki, 2009), sampling for young-of-the-year (YOY) fish was attempted by the MOE’s Sport Fish and Biomonitoring Unit in fall 2008 at the same two locations sampled in 2006 (Grindstone Creek mouth and CCIW sampling location). Again, similar to the 2007 results, YOY shiners were not found by electrofishing at either of the two locations surveyed and as such, there are no Hamilton Harbour YOY fish results for 2008. Reasons for the inability to obtain samples of YOY fish in fall 2008 remain unknown, however, field staff noted that the water level at the Grindstone Creek mouth was extremely low (10-15 cm) and that at the boat ramp near the Burlington Shipping Canal (CCIW sampling location), all that could be found were gobies (S. Petro, 2008, pers. comm.).



3. Results and Discussion

3.1 General Field Observations Many general observations were made about conditions routinely noted at each station during the 2008 field season; these observations may assist in interpretation of results including explanatory factors and may be referred to in each section where appropriate. At Station 268 (Windermere Arm/Basin Bridge), many bubbles rising to the surface of the water were routinely observed, as well as many large fish jumping out of the water, likely carp. The water also had a sewage odour, and routinely had flocs/particles in water samples collected from this station, either due to inputs from Windermere Basin or possibly due to in situ disturbance of the sediments by the fish.

At Station 366 (Strathearne Ave Slip – south end), the boom around the CSO in the southwest corner of the Slip routinely had garbage/debris in it (Figure 12). Additionally, oil sheens in the southern third of the Slip were consistently observed on the water surface during the 2008 season (Figure 13). These sheens varied in size and coverage throughout the five surveys, but were often observed with red-orange globules in the sheen. Small slicks also seemed to form on the water surface following the bursting of bubbles which rose to the surface.

Figure 12: Boom at Strathearne Ave Slip CSO outfall – southwest corner of the Strathearne Ave Slip.



Figure 13: Select photographs of oil sheens observed on the surface of the water at Station 366 during the 2008 field season: June 3 (top left), June 4 (bottom left), September 17 (top right), September 18 (bottom right). At Station 369 (ArcelorMittal Dofasco Boat Slip – mid-slip), the water temperature was noticeably warmer relative to other stations monitored during each survey. At station 370 (Mouth of Windermere Arm – northwest corner of Pier 27 CDF), it was noted that the CDF was not directly open to the Harbour as is shown on some maps, and there was a strong guano odour from the large colony of cormorant at the CDF. In addition to observations that were noted on each sampling event during the 2008 season, a number of date- specific observations of significance were noted. On May 28, when the anchor of the Kemp Boat was pulled-up at Station 370, a clump of ~15 Dreissenid mussels was attached to the anchor (Figure 14). These mussels were tentatively identified as quagga mussels, and individual mussels were very large, each being ~3.5 – 4.5 cm long.



Figure 14: Dreissenid mussels caught on the anchor from Station 370 on May 28, 2008. On June 3, 2008, abundant copepods were present at most stations, except Station 366. Also, there was evidence of a recent sewer overflow event between stations 352, 366 and 268. On August 19, 2008, a large turbidity plume was noted in the northeast corner of the Harbour near the mouth of Indian Creek, as well as a brown turbidity plume in Windermere Arm to the Harbour, and a very sharp-edged brown sediment plume from Grindstone Creek and Cootes Paradise to the Harbour (Figure 15). Further to this last point, the water sample from the beta bottle at Station 367 (1 m from bottom) was noticeably cloudier (Figure 4) than the surface sample. Later in the day, evidence of an overflow event was noted in Windermere Arm between Station 352 and 366. Also on August 19, the water temperature in the ArcelorMittal Dofasco Boatslip was up to 29° C, and noticeably warmer than the other stations, and an algae bloom in the Strathearne Ave Slip was noted – the water was green with flocs in it.



Figure 15: Sediment plumes observed in the Harbour on August 19, 2008 in: the northeast corner of the Harbour (left) and at the west end of the Harbour near the mouth of the Grindstone Creek and the Desjardins Canal (right). A day later on August 20, 2008, there was a very prevalent blue-green algae bloom at Station 258 – neon green lines of algae were noted in the water (Figure 16). The bloom was also seen at Station 367 but diminished, and a heavy blue-green algae bloom was also noted in the southern portion of Strathearne Ave Slip, at and surrounding Station 366. Also on this day at Station 366, a large debris pile (sticks, etc.) were noted near the CSO outfall.

Figure 16: Blue-green algae bloom at Station 258 on August 20, 2008.



On September 17, 2008, a blue-green algae bloom was noted at the CCIW dock, some evidence of a bloom was also noted at Station 268, and blue-green algae were found attached to the SPMD shroud at Station 366 upon retrieval (Figure 17).

Figure 17: Algae blooms observed in the Harbour on September 17, 2008: at the CCIW dock (top left), near Station 268 (top right) and on piece of SPMD shroud removed from Station 366 (bottom left). A day later on September 18, 2008, there was some evidence of a blue-green algae bloom at Station 258, and a heavy blue-green algae bloom at Station 366 and surrounding areas in the Strathearne Ave Slip. The water was thick with green flocs and green streaks were visible on the water surface (Figure 18).



Figure 18: Photographs of algae blooms at Station 366 on September 18, 2008.



3.2 Water Sampling in Hamilton Harbour

3.2.1 Quality Assurance/Quality Control of Water Samples For most of the surveys, water field blanks had low PCB concentrations with a minimum concentration of 0 ng/L on June 3 and a maximum, upper limit concentration of <2.04 ng/L on September 18, 2008 (Table 6). Excluding the September 18 results, field blanks were less than 2 – 9% of sample total PCB concentration depending on the method used to determine PCB concentration. Most PCB congeners in the field blank samples were below their respective detection limits; as such, PCB sample concentration data were not blank corrected. Field blank PCB concentrations were not correlated to the corresponding mean sample PCB concentration (Figure 19), further suggesting that any field blank contamination was primarily due to factors external to PCB concentrations measured in the water column on-site. Table 6: Results of QA/QC field blank total PCB concentration data for summer 2008 water sampling in Hamilton Harbour.

Field Blank Total PCB Concentration

(ng/L)

Sample PCB Concentration3

(ng/L)

Field Blank as % of Sample

Date

Station

Min1 Max2 Min1 Max2 Min1 Max2 May 28 367 0.074 <0.49 5.41 <5.56 1.37 8.8 June 3 352 0 <0.56 21.3 <21.41 0 2.6 August 19 365 0.0028 <0.33 3.61 <3.72 0.08 8.9 September 18 258 0.93 <2.04 4.59 <5.15 20.3 39.6 Notes: 1-“Min” or minimum PCB concentrations were calculated assuming any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was equal to zero for purposes of calculating minimum total PCB concentration; this is a less conservative approach to estimating total PCB concentration from reported PCB congener concentrations. 2- “Max” or maximum PCB concentrations represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration 3 – Sample concentration reported is the mean of sample types 11 and 12 at the station noted.



0

0.5

1

1.5

2

2.5

0 5 10 15 20 25Sample PCB concentration (ng/L)

Fiel

d bl

ank

PCB

con

cent

ratio

n (n

g/L)

Figure 19: Correlation between total PCB concentration in field blanks and total PCB concentration in sample at station of field blank collection.

Field blank results from September 18 were 20 – 40% of sample total PCB concentration and suggest sample contamination; reasons for this remain unknown. The September 18 field blank wasn’t likely switched with another sample as it had the lowest total PCB concentration of all samples submitted to the lab on September 18. Field notes indicate that station 258 was the first station sampled of the day on September 18, and initial samples collected when on station had to be discarded and re-sampled following anchoring as the wind was too strong and pushed the vessel off station. It is unknown if the re-sampling at station 258 on September 18 was related to field blank contamination. Further information on field blanks was obtained from the PCB congener patterns relative to Aroclor patterns and patterns observed for samples from the station where the field blanks were collected (Figure 20). Generally, field blanks collected on May 28, June 3 and August 19 showed some similarity to an Aroclor 1242/1254 pattern, although the pattern showed less similarity to Aroclor profiles when examining the mono- and di-chlorinated biphenyls which may be due to higher volatility of these congeners and greater likelihood to be found in air and/or analytical quantification methods. In addition, the May 28, June 3 and August 19 field blanks are more enriched with less-chlorinated congeners relative to each field blank’s respective samples, suggesting that Harbour water was not likely the direct source of PCBs in the field blanks.



May 28, 2008 Field Blank

0

2

4

6

8

10

12

14

16

18

1 6 16 22 37 44 54 70 81 87 99 110

119

128

137

149

155

167

171

178

187

191

200

203

207

PCB

con

gene

r % o

f tot

al

May 28 Stn 367 Field Blank (max)80%A1242 + 20%A1254aMay 28 Stn 367 Sample type 11May 28 Stn 367 Sample type 12

June 3, 2008 Field Blank

0

2

4

6

8

10

12

14

16

18

1 6 16 22 37 44 54 70 81 87 99 110

119

128

137

149

155

167

171

178

187

191

200

203

207

PCB

con

gene

r % o

f tot

al

Jun 3 Stn 352 Field Blank (max)80%A1242 + 20%A1254aJun 3 Stn 352 Sample type 11Jun 3 Stn 352 Sample type 12

August 19, 2008 Field Blank

0

2

4

6

8

10

12

14

16

18

1 6 16 22 37 44 54 70 81 87 99 110

119

128

137

149

155

167

171

178

187

191

200

203

207

PCB

con

gene

r % o

f tot

al

Aug 19 Stn 365 Field Blank (max)80%A1242 + 20%A1254aAug 19 Stn 365 Sample type 11Aug 19 Stn 365 Sample type 12

September 18, 2008 Field Blank

0

2

4

6

8

10

12

14

16

18

1 6 16 22 37 44 54 70 81 87 99 110

119

128

137

149

155

167

171

178

187

191

200

203

207

PCB

con

gene

r % o

f tot

al

Sep 18 Stn 258 Field Blank (max)70%A1242 + 20%A1254a + 10%A1260Sep 18 Stn 258 Sample type 11Sep 18 Stn 258 Sample type 12

Figure 20: PCB congener patterns for four field blanks collected during summer 2008 relative to PCB congener patterns for Aroclors and water samples from station where field blank was collected. Notes: PCB congener patterns were computed assuming “max” PCB concentrations. “Max” or maximum PCB concentrations represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration

The September 18 field blank PCB congener pattern was different relative to the field blanks collected on the other days; it is also the field blank that demonstrated potential contamination. The PCB congener patterns showed similarity to an Aroclor 1242/1254/1260 pattern, which is significant considering that Aroclor 1260 is comprised of more-chlorinated biphenyls which are not likely to have contaminated the sample through air due to their low volatility. Also, the field blank shows a strong similarity to Aroclor patterns, even for the less-chlorinated biphenyls suggesting that contamination may have been due to a source more closely resembling an Aroclor pattern, rather than due to PCB fate and transport processes (i.e. air transport) which tend to alter typical Aroclor profiles. In addition, the field blank PCB congener profile shows a very strong A1242 signature suggesting contamination may have been due to addition of A1242 to the sample. The September 18 field blank had some similarity for the tetra- and penta-chlorinated biphenyls relative to the sample PCB congener patterns, was highly



enriched in less-chlorinated biphenyls and depleted in more-chlorinated biphenyls relative to the samples from station 258. These results suggest that direct contamination of the field blank by water from station 258 was not the likely source.

PCB and TSS replicates collected at one station per survey demonstrated relatively low variability between samples, although generally the TSS replicates demonstrated higher variability than the PCB sample pairs (Table 7). As a quantitative measure of variability, the coefficient of variation (CV)6 was calculated for each replicate set, with a CV of zero signifying no difference between replicate samples. For the summer 2008 PCB dataset, CVs ranged from 0.008 (Station 366, September 18, sample type 11) to 0.159 (Station 352, June 30, sample type 11) and had an overall median CV of 0.017. For the TSS dataset, CVs ranged from 0.007 (Station 366, September 18, sample type 11) to 0.249 (Station 367, August 19, sample type 11) and had an overall median CV of 0.079. Table 7: PCB and TSS replicate results and calculated coefficient of variation (CV)

Date and Station number

Sample type

Total PCB concentration

(ng/L)

PCB CV

TSS (mg/L) TSS CV

11 <48.4, <53.9 0.076 28.5, 31.4 0.068 May 28 – Station 268 12 <23.3, <22.8 0.017 14.3, 15.2 0.043

11 <4.37, <4.47 0.015 5.1, 4.5 0.088 June 3 – Station 367 12 <4.47, <4.25 0.035 6.7, 7.1 0.041

11 <26.5, <21.3 0.159 8.6, 7.8 0.069 June 30 – Station 352 12 <18.8, <18.4 0.016 3.6, 4.2 0.109

11 <2.86, <2.92 0.015 57.7, 40.4 0.249 August 19 – Station 367 12 <3.18, <3.23 0.011 32.7, 23.6 0.229

11 <106.9, <105.6 0.008 10.3, 10.4 0.007 September 18 – Station 366 12 <37.5, <42.0 0.079 6.0, 7.4 0.148 Notes: Total PCB concentrations were computed assuming “max” PCB concentrations. “Max” or maximum PCB concentrations represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration A QA/QC test using paired Beta Bottle-Glug Glug samples collected from 0.5 m depth was conducted to determine if there was any bias or sampling artefacts from using two different methods to collect water samples during the 2008 field season. A regression analysis in Excel was performed on the paired Beta Bottle and Glug Glug sample data (Figure 21). The slope of the linear regression line was less than 1

6 Coefficient of variation = standard deviation / mean



suggesting a bias of higher PCB concentrations through use of the Glug Glug sampler, a result opposite of that anticipated. The p-value for the slope however, was greater than 0.05 (p-value = 0.068) and as such, the relationship was not significant. There was no significant bias in the results as to whether the samples were collected with a Beta Bottle relative to a Glug Glug sampler. In addition, PCB congener patterns for samples collected through these two sampling techniques map onto one another (Figure 22) further suggesting that sampling technique does not impact PCB data analysis.

y = 0.7456x + 1.1557R2 = 0.8689

0

5

10

15

20

25

0 5 10 15 20 25

Glug Glug PCB concentration (ng/L)

Bet

a B

ottle

PC

B c

once

ntra

tion

(ng/

L)

p-value slope = 0.068p-value intercept = 0.75

Regression

Figure 21: Regression analysis of paired Glug Glug-Beta Bottle water samples collected from 0.5 m depth at various stations in Hamilton Harbour during the 2008 field season.



0

2

4

6

8

10

121

4+10 8 16 19

28+3

3 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

con

gene

r % o

f tot

al

Beta bottle (Jun 3)Glug glug (Jun 3)Beta bottle (Jun 30)Glug glug (Jun 30)Beta bottle (Aug 19)Glug glug (Aug 19)Beta bottle (Sep 18)Glug glug (Sep 18)

Figure 22: PCB congener profiles for paired water samples collected at 0.5 m depth using beta bottle and Glug Glug samplers to examine potential bias between sampling methods Notes: PCB congeners as a % of total were computed assuming “max” PCB concentrations. “Max” or maximum PCB concentrations represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration

3.2.2 Total PCB Water Concentrations For the five water quality surveys conducted during summer 2008, total PCB concentrations varied by survey, station and sample type; total PCB concentrations ranged over two orders-of-magnitude throughout the Harbour between 1.87 ng/L (Station 367, Sample type 11, September 18) to <387.32 ng/L (Station 366, Sample type 12, August 19) (Table 8). Mean total PCB concentrations for the five surveys were lowest at station 365 (3.436 ng/L) and highest at station 369 (113.474 ng/L) for sample type 12 (surface-integrated), and were lowest at station 367 (3.76 ng/L) and highest at station 366 (89.682 ng/L) for sample type 11 (grab 1 m from bottom) (Figure 23). Actual sampling depth in the water column for both sample types 11 and 12 for all stations and surveys are available in Appendix IV: Water Column Profiles and Sampling Depths at Nine Stations for Five Water Quality Surveys, superimposed on corresponding water column temperature, turbidity and DO depth profiles.



Table 8: Total Σ82PCB concentrations (ng/L) for water samples collected from Hamilton Harbour during summer 2008 May 28 June 3 June 30 August 19 September 18 Median of 5

surveys Stn Sample

type Min1 Max2 Min1 Max2 Min1 Max2 Min1 Max2 Min1 Max2 Min1 Max2

12 4.20 <4.35 3.23 <3.50 3.12 <3.28 3.67 <3.85 2.67 <3.21 3.23 <3.5 258 11 4.95 <5.11 6.63 <6.79 2.78 <2.92 3.11 <3.23 6.50 <7.09 4.95 <5.11 12 22.92* <23.04* 18.78 <19.19 14.61 <14.81 105.83 <105.86 21.56 <21.65 21.56 <21.65 268 11 51.04* <51.13* 22.69 <22.77 21.02 <21.22 69.56 <69.64 23.84 <23.94 23.84 <23.94 12 15.05 <15.15 18.72 <18.84 17.71* <18.58* 43.28 <43.31 15.57 <15.63 17.71 <18.58 352 11 7.01 <7.19 23.88 <23.97 23.32* <23.93* 20.98 <21.08 31.45 <31.56 23.32 <23.93 12 3.92 <4.06 3.12 <3.26 1.90 <2.85 3.57 <3.70 2.97 <3.31 3.12 <3.31 365 11 4.52 <4.63 3.96 <4.08 2.23 <3.35 3.64 <3.74 3.09 <3.53 3.64 <3.74 12 52.03 <52.10 28.90 <29.04 30.01 <30.11 387.29 <387.32 39.68* <39.75* 39.68 <39.75 366 11 43.42 <43.56 20.58 <20.70 65.19 <65.41 212.46 <212.49 106.22* <106.25* 65.19 <65.41 12 6.08 <6.25 4.22* <4.36* 3.59 <3.71 3.07* <3.21* 2.38 <2.83 3.59 <3.71 367 11 4.73 <4.86 4.28* <4.42* 2.98 <4.03 2.67* <2.89* 1.87 <2.60 2.98 <4.03 12 3.88 <4.04 3.46 <3.59 4.26 <4.35 3.81 <3.92 3.19 <3.78 3.81 <3.92 368 11 3.20 <3.33 3.11 <3.24 3.37 <3.49 5.06 <5.17 3.05 <3.60 3.2 <3.49 12 131.23 <131.52 116.25 <116.41 63.49 <63.64 108.21 <108.34 147.38 <147.46 116.25 <116.41 369 11 20.73 <20.94 136.13 <136.24 58.23 <58.74 33.70 <33.83 148.79 <148.90 58.23 <58.74 12 8.70 <8.91 12.00 <12.23 5.06 <6.04 29.92 <29.99 11.02 <11.11 11.02 <11.11 370 11 8.22 <8.46 5.30 <5.42 6.32 <7.16 7.36 <8.14 8.10 <8.18 7.36 <8.14 12 32.86 <32.93 - - - - - - - - 372 11 24.69 <24.79 - - - - - - - - 12 11.88 <12.03 12.00 <12.23 5.06 <6.04 29.92 <29.99 11.02 <11.11 Median

all stns 11 7.62 <7.83 6.63 <6.79 6.32 <7.16 7.36 <8.14 8.10 <8.18 1 - “Min” or minimum PCB concentrations were calculated assuming any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was equal to zero for purposes of calculating minimum total PCB concentration; this is a less conservative approach to estimating total PCB concentration from reported PCB congener concentrations. 2 - “Max” or maximum PCB concentrations represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration. * Mean of replicate samples



0

50

100

150

200

250

300

258 268 352 365 366 367 368 369 370 372

Tota

l PC

B c

once

ntra

tion

(ng/

L)

Surface-integratedGrab - 1 m from bottom

Figure 23: Mean total PCB concentrations for each station and sample type for five water surveys during summer 2008. Notes: Total PCB concentrations were computed assuming “max” PCB concentrations. “Max” or maximum PCB concentrations represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration. Error bars represent plus and minus one standard deviation. Data for station 372 only represents one sampling event on May 28.

Few historical water quality data are available in the literature to evaluate whether the highly elevated PCB concentrations in Strathearne Slip (station 366) and ArcelorMittal Dofasco Boat Slip (station 369) have been observed in the past, however, some historical PCB water quality data exist for the Strathearne Slip as well as Windermere Basin and Arm. PCB concentrations in the Strathearne Slip prior to the mid-1980s were measured at concentrations of 0.46 to 5.3 ug/L and as high as 180 ug/L in oil residues (MOE, 1985) suggesting that although present concentrations are highly elevated, they have likely undergone a decline from historically even higher concentrations. Additionally, a monitoring study conducted prior to the mid-1980s found a maximum PCB concentration of 90 ug/L in Windermere Basin water (Harlow and Hodson, 1988, p.40). This historical maximum concentration is also much higher than



the 2008 maximum PCB concentration at station 268 of 106 ng/L; also suggesting a decline of PCB concentrations over time in Windermere Basin. However, another study conducted in 1984 found PCB concentrations of 214 ng/L and 86 ng/L in southern Windermere Arm (Mudroch et al., 1989) similar to concentrations measured during the 2008 field season, suggesting that an ongoing source may be present in the Windermere Arm area. The reason(s) for the inconsistency in historical PCB concentrations in the Windermere Arm area are unknown, making the interpretation of relative differences to present conditions challenging.

Firstly, comparison of historical and present PCB concentrations in water should be made with caution as comparability of historical PCB analytical methods to present methods cannot be confirmed. Additionally, contaminants in water have high temporal and spatial variability and one grab sample is likely not representative of ongoing conditions, which was a driving factor in deploying SPMDs during the 2008 field season (3.3 Semi-Permeable Membrane Device (SPMD) Deployment in Hamilton Harbour). While the presence of ongoing sources cannot be eliminated at this point, the observation of increasing PCB concentrations with depth in Windermere Arm surface sediment (Labencki, 2008) suggest ambient PCB concentrations have declined over time. Nonetheless, current total PCB concentrations in Hamilton Harbour, and Windermere Arm in particular, remain problematic.

All PCB concentrations measured in Hamilton Harbour waters during 2008 were above the provincial water quality objective (PWQO) of 1 ng/L (MOEE, 1994). Stations 366 and 369 had mean PCB concentrations in surface-integrated samples over two orders-of-magnitude above the PWQO, and concentrations on par with a Lake Michigan PCB spill site (100-450 ng/L; WHO, 1976 in Erickson, 1997) and concentrations which have been considered representative of highly polluted rivers (<500 ng/L; WHO, 1976 in Erickson, 1997). Total PCB concentrations at Windermere Arm stations are well above background levels for waters in the Great Lakes region.

3.2.3 TSS Water Concentrations

TSS concentrations were generally less variable than PCB concentrations in the Harbour, and ranged over one order-of-magnitude during summer 2008 between 1.8 mg/L (Station 368, Sample type 11, June 30) and 49.1 mg/L (Station 367, Sample type 11, August 19) (Table 9). Mean total TSS concentrations for the five surveys were lowest at station 258 (3.18 mg/L) and highest at station 367 (10.38 mg/L) for sample type 12 (surface-integrated), and were lowest at station 368 (3.16 mg/L) and highest at station 268 (17.96 mg/L) for sample type 11 (grab 1 m from bottom) (Figure 24). Mean TSS concentrations were consistently higher in bottom grab samples relative to surface integrated-samples at each station, except for stations 368, 370 and 372.



TSS concentrations were monitored during summer 2008 to provide interpretation in the PCB water concentration results as PCBs, particularly more-chlorinated congeners, have an affinity to bind to suspended particles in the water column. Turbidity profiles in Appendix IV: Water Column Profiles and Sampling Depths at Nine Stations for Five Water Quality Surveys, provide further interpretation on TSS data, as they approximate the thickness of suspended sediment plumes in the water column and whether the TSS data may be reflecting in situ sediment resuspension such as due to vessel traffic or storms. Storms however may also bring in external sources of suspended sediment from the watersheds, in addition to in situ resuspension. For such reasons, interpretation of TSS data may provide context of PCB dynamics, trends and source interpretation.

0

5

10

15

20

25

30

35

40

258 268 352 365 366 367 368 369 370 372

TSS

conc

entr

atio

n (m

g/L)

Surface-integratedGrab - 1 m from bottom

Figure 24: Mean TSS concentrations for each station and sample type for five water surveys during summer 2008. Notes: Error bars represent plus and minus one standard deviation.



Table 9: TSS concentrations (mg/L) for water samples collected from Hamilton Harbour during summer 2008 Station Sample

type May 28 June 3 June 30 August 19 September 18 Median of 5

surveys 12 4.4 2.6 3.1 3.6 2.2 3.1 258 11 4.4 5.0 2.5 5.2 9.1 5.0 12 14.8* 6.7 4.4 6.7 6.5 6.7 268 11 30.0* 7.2 9.8 33.3 9.5 9.8 12 4.5 4.6 3.9* 6.3 5.9 4.6 352 11 3.8 6.7 8.2* 6.7 8.7 6.7 12 2.9 3.0 2.6 4.5 3.1 3.0 365 11 5.5 3.7 2.4 3.9 4.5 3.9 12 7.8 4.8 4.6 7.1 6.7* 6.7 366 11 11.1 4.9 8.9 10.8 10.4* 10.4 12 4.4 6.9* 6.4 28.2* 6.0 6.4 367 11 6.3 4.8* 7.8 49.1* 6.1 6.3 12 3.4 2.2 2.9 4.1 3.5 3.4 368 11 2.6 2.1 1.8 6.0 3.3 2.6 12 3.3 7.9 4.3 5.0 5.7 5.0 369 11 4.4 9.3 3.7 4.8 19.4 4.8 12 4.0 2.9 2.8 7.9 4.2 4.0 370 11 4.8 2.3 3.0 3.6 3.6 3.6 12 8.0 - - - - 372 11 7.1 - - - - 12 4.4 4.6 3.9 6.3 5.7 Median all

stations 11 5.2 4.9 3.7 6.0 8.7 * Mean of replicate samples



3.2.4 TSS-Total PCB Correlations and Regressions Correlations and regression equations between TSS and total PCB concentrations were investigated for sample type pooled data at each station to examine the potential role of suspended sediment in driving ambient PCB concentrations. Generally, a positive correlation between TSS and PCB concentrations was observed at most stations for both surface-integrated samples and bottom grab samples (Figure 25). However, a number of exceptions and outliers were also evident and many of the regression equations were not significant (Table 10), in some cases likely due to the presence of an outlier. The slope of the TSS-PCB regression equations were significant at stations 258, 352, 365, 368, and 370 and were not significant at stations 268, 366, 367 and 369. Important to note however is that although the slope was significant at stations 352 and 365, R2 was low meaning resuspension is playing a role but factors other than TSS are also important in determining total PCB concentrations. Table 10: TSS-PCB regression equations by station Station Linear regression

equation R2 p-value

intercept p-value slope

258 y = 0.597X + 1.817 0.63 0.0409 0.006 268 y = 1.016X + 22.59 0.15 0.1214 0.2093 352 y = 2.900X + 4.555 0.34 0.5813 0.04819 365 y = 0.3555X + 2.367 0.48 0.0013 0.02623 366 y = 11.41X + 4.92 0.068 0.965 0.412 367 y = -0.032X + 4.35 0.28 1.63E-08 0.0515 368 y = 0.399X + 2.58 0.72 2.36E-05 0.0018 369 y = 5.21X + 61.24 0.27 0.0378 0.1219 370 y = 4.034X – 5.17 0.81 0.110 0.000374 Notes: Regression performed in Excel using maximum or upper limit total PCB concentrations (congeners < detection assumed equal to detection). P-values <0.05 are in bold. Both surface-integrated and bottom grab sample data were pooled for each station to generate regression equation.



Station 258

0

1

2

3

4

5

6

7

8

0 2 4 6 8 10TSS (mg/L)

Tota

l PC

B (n

g/L)

Grab - 1m from bottom

Surface-integrated

Station 268

0

20

40

60

80

100

120

0 5 10 15 20 25 30 35TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated

Station 352

05

101520253035404550

0 2 4 6 8 10TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated

Station 365

00.5

11.5

22.5

33.5

44.5

5

0 1 2 3 4 5 6TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated

Station 366

0

50

100

150

200

250

300

350

400

450

0 2 4 6 8 10 12TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated

Station 367

0

1

2

3

4

5

6

7

0 10 20 30 40 50 60 70TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated

Station 368

0

1

2

3

4

5

6

0 1 2 3 4 5 6 7TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated

Station 369

0

20

40

60

80

100

120

140

160

0 5 10 15 20 25TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated



Station 370

0

5

10

15

20

25

30

35

0 2 4 6 8 10TSS (mg/L)

Tota

l PC

B (n

g/L)


Surface-integrated

Figure 25: Correlation between TSS and PCB concentration at each station for five surveys during summer 2008.

For the stations where the regression analysis did not find a significant positive relationship between TSS and total PCB (Table 10), this lack of positive relationship was clearly obvious in the correlation for stations 367 and 369 (Figure 25), but a positive relationship does appear to exist at stations 366 and 268 despite a lack of significance in the regression equations for these stations. These two stations along with station 352 are all stations in Windermere Arm and each had an outlier that in each case corresponds to the surface-integrated sample collected at each station on August 19.

On the August 19 sampling event, TSS concentrations at stations 268, 352 and 366 varied little between one another (6.7, 6.3 and 7.1 mg/L, respectively) while PCB concentrations demonstrated relatively high variation (105.9 ng/L, 43.3 ng/L and 387.3 ng/L, respectively); PCB concentrations in water at these stations appear to be elevated relative to the TSS concentrations present. While there are many potential explanatory factors for the presence of these PCB concentration outliers on August 19, it is worth noting that this event was sampled following a rain event on August 18, the largest antecedent rain event (16.2 mm) for all five surveys conducted during summer 2008 (Appendix I: May – September 2008 weather conditions in Hamilton) suggesting potential PCB inputs from the watersheds.

While the positive correlations and significant regressions at most stations suggest that suspended sediment plays a role in resultant ambient PCB concentrations in water, the exceptions and outliers in Windermere Arm stations in particular suggest drivers other than suspended sediment (and resuspension), which may be playing a more localized effect on PCB dynamics in the waters of Hamilton Harbour, such as a high dissolved phase PCB or presence of PCB in a non-aqueous phase.



3.2.5 Theoretical PCB Concentration on Suspended Sediment and Comparison to Surface Sediment While regressions between paired TSS and PCB concentrations in water samples are a line-of-evidence in investigating the role of suspended sediment in ambient PCB concentrations in the water column (3.2.4 TSS-Total PCB Correlations and Regressions), such an analysis does not account for the source of the particles. To further gauge the potential role of resuspension of in situ sediments at each of the stations surveyed in 2008, the theoretical PCB concentration on suspended sediment was calculated assuming all PCBs measured in the water column were bound to the measured TSS. This theoretical suspended sediment PCB concentration was then compared to recent measured PCB concentrations in surface sediment (Figure 26; Table 11).

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

258 268 352 365 366 367 368 369 370 372

Theo

retic

al P

CB

con

cent

ratio

n on

sus

pend

ed

sedi

men

t (ng

/g)

Mediantheoreticalsuspendedsediment[PCB] ng/g

Measuredsurfacesediment[PCB] ng/g

Stn 366 Max: 54,552 ng/g

Stn 369 Max: 39,853 ng/g

Figure 26: Theoretical PCB concentrations on suspended sediment relative to measured PCB concentrations in surface sediment. Notes: Theoretical PCB concentrations on suspended sediment calculated assuming all PCBs measured in water column during summer 2008 surveys were bound to measured sediment concentrations. Total PCB concentrations were calculated using maximum or upper limit total PCB concentrations (congeners < detection assumed equal to detection). For station 372, values represent only two samples collected on May 28, 2008. For “PCB concentration in surface sediment”, values represent the mean of samples if n>1, otherwise, values represent single replicate. Error bars on theoretical suspended sediment PCB concentration represent the minimum (lower limit) and maximum (upper limit) as presented in Table 11.



Table 11: Theoretical PCB concentrations on suspended sediment for five surveys conducted during summer 2008. Theoretical suspended sediment [PCB] (ng/g)

Measured surface sediment Station

Min Median Max [PCB] (ng/g)

Date of sampling

Data source

[theoretical]/ [measured]

258 621 1116 1458 513 Aug 2006 Stn 258 - MOE database 1.2 – 2.8 x 268 1497 2342 15,800 600 Aug 2000 Stn 268 - MOE database 2.5 – 26.3 x 352 1891 3472 6874 1085 Dec 2003 Stn 352 - MOE database 1.7 – 6.3 x 365 785 1077 1399 220 April 2005 Stn 365 - MOE database 3.6 – 6.4 x 366 3925 6612 54,552 16,000 Aug 2008 Stn 366 - MOE database 0.2 – 3.4 x 367 50 548 1421 170 Dec 2003 Stn WABA04 - MOE

database 0.3 – 8.4 x

368 862 1235 1941 970 Oct 2000 Stn 7019 in Milani and Grapentine (2006a)

0.9 – 2.0 x

369 4759 14,768 39,853 9500 1999 Stn T4-M in Jaagumagi et al. (2003)

0.5 – 4.2 x

370 1762 2322 4217 700 Aug 2000 Stn 004 - MOE database 2.5 – 6.0 x 372 3492 3804 4117 2250 Nov 2002 Stn WA19 in Milani and

Grapentine (2006b) 1.6 – 1.8 x

Notes: Theoretical PCB concentrations on suspended sediment calculated assuming all PCBs measured in water column during summer 2008 surveys were bound to measured sediment concentrations. Total PCB concentrations were calculated using maximum or upper limit total PCB concentrations (congeners < detection assumed equal to detection). For station 372, values represent only two samples collected on May 28, 2008. For “PCB concentration in surface sediment”, values represent the mean of samples if n>1, otherwise, values represent single replicate.



The theoretical PCB concentrations on suspended sediment ranged over three orders-of-magnitude from 50 ng/g (minimum; Station 367) to 54,552 (maximum; station 366). While the intention of this analysis is to provide evidence in potential source identification, it should also be noted that the maximum theoretical PCB concentration on suspended sediment at station 366 exceeds 50 ppm (50,000 ng/g), the threshold which defines PCB waste under Ontario Regulation 362 of the Environmental Protection Act (MOE, 2007). While the calculated PCB concentration of 54,552 ng/g at station 366 remains theoretical in nature, any follow-up work in the Strathearne Ave Slip should note the potential for the presence of hazardous waste at this station, that is, actual sediment samples have the potential to have PCB concentrations above the 50 ppm benchmark and caution should be exercised. This issue is in addition to potential bioaccumulation and biomagnification of PCBs in the local foodweb, the main issue underscoring this report as it pertains to the BUI Restrictions on Fish and Wildlife Consumption.

It is an oversimplification to assume that all PCBs in the water column are bound to sediment as it is likely that some PCBs are in the dissolved phase in the water column. As such, the theoretical PCB concentration on suspended sediment should be substantially greater than the measured surface sediment PCB concentration for PCBs in the water column to be due to ex situ contamination or a non-sediment PCB source. Stations where the theoretical PCB suspended sediment concentration was substantially greater than the PCB concentration measured in surface sediment (measured surface sediment PCB concentration was less than the lower error bar of the theoretical PCB concentration of suspended sediment; Figure 26) are stations 258, 268, 352, 365, 370 and 372. Conversely, stations where the measured PCB concentration in surface sediment was greater than the minimum theoretical PCB suspended sediment concentration were stations 366, 367, 368 and 369.

This analysis suggests that for most stations monitored in 2008 (258, 268, 352, 365, 370, 372), the PCB concentration in surface sediment is not high enough to completely explain the theoretical PCB concentration on suspended sediment assuming most PCB is sediment-bound; these stations either have a high proportion of their PCB concentration attributable to the dissolved phase or a PCB source other than resuspension of in situ sediments may be contributing to measured total whole water PCB concentrations. For the remaining stations (366, 367, 368 and 369), the measured PCB concentration in surface sediment is high enough to explain measured whole water concentrations, meaning resuspension of in situ sediment is a potential source of PCBs in the water column at these sites. Determining the actual PCB dynamics at stations 367 and 368 however is of a lower priority as these stations had measured PCB concentrations in surface sediment in line with background levels measured in other areas of the Harbour (Table 11). While measured PCB concentrations in surface sediment at stations 366 and 369 are high enough to support theoretical PCB concentrations in suspended sediment, a



significant regression between PCB and TSS concentrations were not found for these stations (3.2.4 TSS-Total PCB Correlations and Regressions), suggesting that any elevated measured PCBs in the water column are not entirely a result of elevated TSS concentrations. Further, a unique observation at station 366 is that the measured PCB concentration in surface sediment is greater than the median theoretical PCB concentration in suspended sediment, while the converse is true for all other stations, including station 369 (Figure 26). Important to note however is the very large range in theoretical PCB concentrations on suspended sediment at station 366 (3,925 ng/g – 54, 552 ng/g), making any further interpretation of this anomaly difficult.

In contrast to stations 366 and 369, stations 258 and 370 had significant PCB-TSS regressions with high R2 values and theoretical PCB suspended sediment concentrations much greater than measured surface sediment concentrations suggesting that ex situ sediment-bound PCBs are a driver of whole water PCB concentrations at these stations. At stations 366 and 369 however, analysis thus far suggests that both an ex situ source of PCBs and resuspension of in situ surface sediment cannot be eliminated as drivers of elevated PCB concentrations in these slips. Thus, PCB dynamics at stations 366 and 369 remain complex and potentially significant in terms of being overall Harbour PCB sources; further analysis of PCB dynamics at these stations is recommended, and detailed turbidity profiles are investigated in the following Section 3.2.6 Variability of Total PCB Concentrations with Depth in the Water Column at Each Station.

3.2.6 Variability of Total PCB Concentrations with Depth in the Water Column at Each Station Paired water samples (sample type 11; sample type 12) were collected at each station during each of the five surveys to determine if total PCB concentrations were higher at the surface or 1 m above the sediment bed. This data analysis was particularly important for examining the potential role of resuspension as a primary contributor to PCB concentrations in the water column. A two-tailed matched pairs t test was performed for each station (5 matched pairs), and for the Harbour in general by pooling all 45 matched pairs (Table 12); a caution to this test is that it assumes that the dataset is normally distributed7. 7 A nonparametric test cannot be conducted as n has to be 10 or greater.



Table 12: Matched paired t test for two sample types at each station during summer 2008 Station Mean d Standard error t matched pairs p-value* 258 1.39 0.93 1.49 0.2105 268 0.83 10.4 0.08 0.9401 352 -0.76 6.6 -0.12 0.9103 365 0.43 0.14 3.15 0.0345 366 -18.0 41.7 -0.43 0.6893 367 -0.31 0.29 -1.07 0.3449 368 -0.17 0.38 -0.45 0.6760 369 -33.7 25.0 -1.35 0.2484 370 -6.2 4.1 -1.49 0.2105 All stations pooled

-6.3 5.3 -1.18 0.2443

Notes: di, the difference for matched pair i, was determined by subtracting sample type 12 from sample type 11. As such, a positive mean d value indicates that total PCB concentration was on average higher in sample type 11 (1 m from sediment bed) relative to sample type 12 (surface-integrated). *p-value for a two-tailed test from http://www.danielsoper.com/statcalc/calc08.aspx. P-values less than 0.05 are shown in bold. Total PCB concentrations were calculated using maximum or upper limit total PCB concentrations (congeners < detection assumed equal to detection). For all stations except station 365, the difference in total PCB concentration between sample types was not significant during summer 2008 suggesting that resuspension was not a consistent contributor of PCBs to the water column in the Harbour. For all five surveys at station 365, the grab samples collected 1 m from the sediment bed (sample type 11) were greater than the surface-integrated samples (sample type 12), albeit, the total PCB concentration difference between the matched pairs was relatively small (<1 ng/L or ~20%) and the turbidity profiles did not indicate consistent strong increases in turbidity with depth (Appendix IV: Water Column Profiles and Sampling Depths at Nine Stations for Five Water Quality Surveys). Additionally, because the total PCB concentrations were low at station 365 relative to high concentrations consistently measured in Windermere Arm stations (Figure 23), focus on station 365 in particular due to this statistical result is not warranted given the objective to understand the overall PCB fate and transport mechanisms occurring in the Harbour.

It is also important to emphasize that the matched pairs t test did not test whether or not resuspension was occurring, but rather, if resuspension was the primary and consistent contributor of PCBs in the water column relative to other potential sources; the test only compares the relative difference between surface-integrated samples and bottom samples. In this sense, resuspension of PCB-contaminated sediment could be high but may not be indicated as a primary source through the matched pairs t test



(Table 12) if other potential PCB sources were also equally high in contributing PCBs to the surface of the water column. Additionally, because the test was based on five matched pairs corresponding to the five surveys, resuspension could have been sporadic and significant during only one or two of the events (e.g. due to ship traffic, storms, etc.), which would not be reflected in the statistical results in Table 12.

As such, all matched pairs where the bottom grab sample total PCB concentration was greater than the surface-integrated sample concentration were investigated qualitatively, and turbidity profile data (Appendix IV: Water Column Profiles and Sampling Depths at Nine Stations for Five Water Quality Surveys) as well as PCB congener profiles (Figure 27) were used to support further evaluation of the potential role of resuspension during such events. As sediment in the Harbour has a strong Aroclor 1254g/1260 profile (Labencki, 2008; Figure 27), water samples more strongly influenced by resuspension of PCB contaminated sediment should demonstrate enrichment of more-chlorinated PCB congeners. Further, high proportions of congeners 138, 149 and 153+168 relative to Aroclor profiles were observed across all stations in the Harbour suggesting a unique Harbour profile likely sourced from historically-contaminated sediments in the Harbour.

Station 258 - Sample type 11

0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3Jun 30Aug 19Sep 1820%A1242+40%A1254g+40%A1260


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al



0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28 (1)May 28 (2)Jun 3Jun 30Aug 19Sep 1840%A1242+20%A1254g+40%A1260


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28 (1)May 28 (2)Jun 3Jun 30Aug 19Sep 1840%A1242+20%A1254g+40%A1260A1242




0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3Jun 30 (1)Jun 30 (2)Aug 19Sep 1820%A1242+40%A1254g+40%A1260


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3Jun 30 (1)Jun 30 (2)Aug 19Sep 1820%A1242+40%A1254g+40%A1260A1242


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al



0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al



0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3Jun 30Aug 19Sep 18 (1)Sep 18 (2)60%A1242+20%A1254g+20%A1260A1242


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3Jun 30Aug 19Sep 18 (1)Sep 18 (2)60%A1242+20%A1254g+20%A1260A1242




0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3 (1)Jun 3 (2)Jun 30Aug 19 (1)Aug 19 (2)Sep 1820%A1242+40%A1254g+40%A1260


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3 (1)Jun 3 (2)Jun 30Aug 19 (1)Aug 19 (2)Sep 1820%A1242+40%A1254g+40%A1260


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al



0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al



0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28Jun 3Jun 30Aug 19Sep 1810%A1242+20%A1254g+70%A1260A1260


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al





0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al



0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al


Station 372 - Sample type 11 & 12

0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28 (type 11)May 28 (type 12)30%A1242+40%A1254g+30%A1260

PCB Congener Patterns in Surface Sediment

0

2

4

6

8

10

12

18 28 44 54 77 95 104

114

123

138

153

157

168

171

180

188

194

202

208

PCB

con

gene

r % o

f tot

al

Station 352 (sampled Dec 2003)Station 365 (sampled April 2005)Station 258 (sampled August 2006)50% A1254g + 50% A1260

Figure 27: PCB congener patterns for two sample types at each station during five surveys conducted during 2008 relative to Aroclor and sediment PCB congener profiles. Notes: Total PCB concentrations were calculated using maximum or upper limit total PCB concentrations (congeners < detection assumed equal to detection). As different analytical methods were used to determine PCB congener concentrations in water relative to sediment, caution should be used in direct comparison of congener patterns between matrices as 82 congeners are analyzed for water, and 55 for sediment. Also note that the analytical method for water includes mono- and di-chlorinated biphenyls whereas the method for sediment does not include these homologues. Aroclor profiles from US EPA (2006). At station 258, total PCB concentrations in grab samples collected 1 m from bottom (sample type 11) were greater than surface-integrated samples (sample type 12) on May 28, June 3 and September 18; however, the difference between the pairs on May 28 was relatively small (~15%; 0.76 ng/L). On June 3 and September 18, total PCB concentrations from the bottom grab samples were approximately two times greater than surface-integrated samples. For these two surveys, the profiles indicated higher turbidity near the sediment bed relative to the upper water column, and close to the sediment bed there was a marked increase in turbidity with depth suggesting resuspension of bottom sediments during these surveys. The PCB congener profiles however did not demonstrate any anomalies for these survey dates, meaning that if



resuspension was particularly high on June 3 and September 18, it contributes towards the background PCB concentrations at the site on an ongoing basis. On the other hand, a higher proportion of less-chlorinated congeners in surface-integrated samples relative to bottom grab samples was evident at station 258, particularly for the August 19 and September 18 surveys, suggesting PCB contributions from a process other than resuspension in the upper water column. At station 268, total PCB concentrations were greater in bottom samples during all surveys except August 19. Generally, station 268 demonstrated an increase in turbidity with depth suggesting that resuspension of bottom sediments may be contributing PCBs to the water column; however, a very strong increase in turbidity with depth also occurred on August 19. While the total PCB concentration in the bottom sample was very high during this survey, and in fact, the highest of all surveys at this station for this sample type (69.6 ng/L), the surface-integrated sample concentration during this survey was even higher (105.9 ng/L). Thus, results suggest that resuspension may play an ongoing role in contributing PCBs to the water column at station 268, but that sporadic events other than resuspension which impact the upper water column may play an even larger role when they occur. The PCB congener profiles are consistent with this explanation of PCB dynamics at this site as an anomalous PCB congener pattern was evident during the August 19 survey for both sample types. The high proportions of less-chlorinated congeners observed on August 19 throughout the water column suggest a PCB input other than resuspension of surface sediment. Similar to station 268, turbidity at station 352 increased with depth except on May 28. Correspondingly, total PCB concentrations were greater in bottom samples during all surveys except May 28, and also August 19. While reasons for higher PCB concentrations in the surface sample on August 19 might be due to the same phenomenon which impacted station 268 during the same survey (supported by a similar anomalous PCB congener signature enriched in less-chlorinated congeners), also important to note is that the bottom grab sample on August 19 at station 352 was collected just below the turbidity “lens” observed during this event which may also play a role in the results. Nonetheless, results suggest that resuspension of PCB-contaminated bottom sediment may be occurring fairly consistently, also supported by slightly higher proportions of more-chlorinated congeners in bottom grab water samples relative to surface-integrated samples. However, the possibility remains that sporadic events other than resuspension which impact the upper water column may also be playing a relatively significant role. Turbidity at station 366 was erratic, with different patterns with depth observed during each survey so few generalities can be made for this station. Total PCB concentrations were greater in bottom samples relative to surface-integrated samples only during the June 30 and September 18 surveys. While a strong increase in turbidity with depth was observed on June 30, the increase in turbidity with depth was less so on



September 18. Also important to note is that an increase in turbidity with depth was observed on May 28, although total PCB concentrations were higher in surface-integrated samples both at station 366 and nearby station 372, where there was no clear increase in turbidity with depth. Results from station 366 suggest that while resuspension of PCB-contaminated bottom sediments may occur sporadically, supported by higher proportions of more-chlorinated congeners in the bottom grab samples relative to the surface-integrated samples (at both stations 366 and 372), a process other than resuspension appears to be driving the high PCB concentrations in the upper portion of the water column at station 366. High proportions of mono- through tri-chlorinated biphenyls were consistently measured in both sample types from station 366, a PCB signature not as stongly associated with particles due to the higher solubility of these congeners. Also interesting at station 366 were high turbidity concentrations in the mid-water column observed on June 3 and August 19; a similar pattern was observed on August 19 at station 352. The process(es) responsible for these turbidity “lenses” are unknown, but may include responses to weather events or vessel activity. At station 367, total PCB concentrations were higher in bottom samples relative to surface-integrated samples during the June 3 and June 30 surveys, although the difference in PCB concentrations between the sample types was relatively small (<10%) and likely within sampling and laboratory error. During these two surveys, turbidity was not greater in the bottom grab sample relative to the surface suggesting resuspension of bottom sediments was not likely playing a role in the results. Also, a strong increase in turbidity with depth was observed on August 19 and September 18 which did not appear to impact the PCB concentration results, although the bottom grab sample on September 18 was collected just above the depth where turbidity was greatest. In addition, there was little difference in the PCB congener signature between sample types at station 367, although higher proportions of less-chlorinated congeners were evident in the surface-integrated samples particularly for the August 19 and September 18 surveys, similar to that observed for nearby station 258. Thus, any resuspension of bottom sediments at station 367 does not appear to be playing a role in the PCB concentrations at this site. Total PCB concentrations at station 368 were higher in the paired bottom grab sample only on August 19; for the rest of the surveys, PCB concentrations were higher in the surface-integrated samples. Correspondingly, the turbidity profiles for station 368 demonstrated relatively uniform turbidity with depth, except on August 19 when a large increase in turbidity was observed close to the bottom. However, the relative difference in total PCB concentration between the two paired samples was small (~25%). Important to note is that the bottom grab sample on August 19 was collected just below the turbidity peak in the water column, which may explain why a relatively higher total PCB concentration was not observed during this survey despite the high turbidity at depth. Nonetheless, the total PCB concentration for all sample types and events (including August 19) were relatively low, and PCB congener profiles differed little between sample types (except for higher proportions of less-chlorinated congeners in



the surface-integrated samples, akin to stations 258, 367) suggesting resuspension of bottom sediments was not likely playing a large role in the results. At station 369, total PCB concentrations were higher in bottom grab samples relative to the surface-integrated samples during the June 3 and September 18 surveys, albeit the difference was small (<1%) between the sample types on September 18. Turbidity profiles demonstrate a clear increase with depth during the June 3 and September 18 surveys, although important to note is that the bottom grab sample on September 18 was collected just above the sharp increase in turbidity observed around 7 to 8 m depth; this may be why a relatively higher PCB concentration for sample type 11 was not measured on September 18. Similarly, a large spike in turbidity was also observed near the bottom during the June 30 survey, however, the bottom grab sample was collected below this spike, which may be why higher PCB concentrations were not observed for the bottom grab sample relative to the surface-integrated sample during this event. Clear increases in turbidity with depth were not observed during the May 28 and August 19 events; PCB concentrations during these surveys were much higher in the surface-integrated samples relative to the bottom grab samples.

PCB fate and transport processes in the ArcelorMittal Dofasco Boatslip have been studied in the past due to known sediment contamination in the Slip. Studies conducted in the Slip during the 1990s found that sediment resuspension in the slip due to ship traffic was significant as “[s]hip movement significantly increases water turbidity due to sediment resuspension…[and r]e-suspension of sediment can re-entrain contaminants into the water column and result in movement of contaminants down the boat slip” (Jaagumagi et al., 2003, p. 6). An intensive study conducted in 1995 in the Slip demonstrated significant sediment resuspension with passage of commercial vessels and that the estimated depth of bed erosion was 1 – 8 mm due to a passing ship (Irvine et al., 1997).

Empirical evidence of in situ bottom sediment resuspension due to ship traffic during the 2008 survey may have been observed on June 3 as the Algontario departed the Slip at 9:15 a.m. (HPA, 2008), and station 369 was sampled at 10:30 a.m., just over an hour later. The turbidity profile for station 369 on June 3 shows an increase in turbidity with depth, and the TSS concentration for the bottom grab sample was approximately twice the concentration relative to the other surveys, except for the September 18 survey (Table 9). Also, although there is little difference in PCB congener signature between the bottom grab and surface-integrated samples, the PCB congener signature in water samples from station 369 are consistently enriched in more-chlorinated congeners relative to other stations in the Harbour (3.2.8 Spatial Variability of PCB Water Concentrations in the Harbour).

While there are many explanatory factors for higher PCB concentrations at depth during some surveys such as observed on June 3, impacts of ship traffic on contaminated bottom sediments should be considered. While resuspension may be an



important process at station 369 for contributing PCBs to the water column as demonstrated historically (Jaagumagi et al., 2003; Irvine et al., 1997) and through empirical data in this study, other factors may be simultaneously at play to drive the high PCB concentrations observed in the upper portion of the water column at this station, although consistent entrainment of resuspended sediment into the water column may also be occurring. Total PCB concentrations at station 370 were higher in the bottom grab sample relative to the surface-integrated sample only on June 30, although the difference between the paired samples was relatively small (~15%). The turbidity profiles at station 370 were erratic, with different profiles observed among the surveys; nonetheless, the turbidity where the bottom grab samples were collected was generally not greater than that observed at the surface. During a few surveys (June 30, August 19), turbidity was greatest in mid-water column. These turbidity “lenses” were also observed at stations 268, 366 and 352 on August 19, suggesting a relatively strong hydraulic connection between these stations if these mid-water column turbidity “lenses” were formed through the same process. The PCB congener signature differed little between bottom grab and surface-integrated samples, although there appeared to be slightly higher proportions of more-chlorinated congeners in the surface-integrated samples relative to bottom grab samples, suggesting that sediment-bound PCB inputs are not likely due to resuspension of in situ materials. Also of note, high proportions of less-chlorinated congeners were observed in surface-integrated samples during the August 19 survey, likely due to the same process which also impacted stations 352 and 268. Overall, the lower PCB concentrations at depth relative to the surface, the lack of clear increase in turbidity with depth and PCB congener signatures suggest that resuspension of in situ bottom sediments at station 370 does not appear to be playing a role in the PCB concentrations at this site. In summary, resuspension of in situ bottom sediment does not appear to be a consistent source of PCBs to the water column on a Harbour-wide basis, however, there is empirical evidence that it may contribute towards elevated PCB concentrations sporadically in localized areas of the Harbour, which after mixing, may form background conditions in the Harbour. These localized regions where PCB concentration does appear to be related to resuspension on occasion may be important sources to the overall PCB dynamics of the Harbour, such as resuspension of PCB-contaminated bottom sediments in Windermere Arm. Previous studies have found that Windermere Arm sediment is very soft and therefore erodable (Krishnappan and Droppo, 2006), and due to a finding of resuspension and redistribution of sediment-derived contaminants, Slater et al. (2008) recommended immobilization of Windermere Arm sediment. Nonetheless, data from the 2008 survey demonstrates that resuspension is likely not the only contributor playing a role in the ambient PCB water concentrations in the Harbour, consistent with conclusions from Section 3.2.4 TSS-Total PCB Correlations and Regressions and 3.2.5 Theoretical PCB Concentration on Suspended Sediment and Comparison to Surface Sediment. On multiple occasions and at several stations,



PCB concentrations were elevated in the surface-integrated sample relative to the bottom grab sample. This gradient in the water column could potentially be due to direct inputs of PCB-contaminated waters at the surface, or could be related to oil sheens if present (e.g. station 366; see Section 3.1 General Field Observations).

3.2.7 Temporal Variability in PCB and TSS Concentrations

Resuspension of in situ sediments are not likely the sole driver of ambient PCB concentrations in Hamilton Harbour, and to further investigate the PCB dynamics in the Harbour and the consistency of PCB source(s), the temporal variability of total PCB concentrations and PCB congener profiles at each station were examined. The temporal variability in total PCB water concentrations can also be compared to the temporal variability of paired TSS concentrations at each station for additional context (Table 13). Table 13: Variability in PCB and TSS concentrations in the water column expressed as a ratio of the highest concentration to the lowest concentration at each station for the five surveys conducted during summer 2008.

Sample type 12 Sample type 11 Station PCB TSS PCB TSS

258 1.4 2.0 2.4 3.6 268 7.1 3.4 3.3 4.6 352 2.9 1.6 4.4 2.3 365 1.4 1.7 1.4 2.3 366 13.3 1.7 10.3 2.3 367 2.2 6.4 1.9 10.2 368 1.2 1.9 1.6 3.3 369 2.3 2.4 7.1 5.2 370 5.0 2.8 1.6 2.1

PCB concentrations for surface-integrated samples were most variable at stations 366, 268 and 370, and for bottom grab samples, most variable at stations 366, 369 and 352; all of these stations are located in Windermere Arm. PCB concentrations for surface-integrated samples were the least variable at stations 368, 258, and 365, and for bottom grab samples, least variable at stations 365, 368, 370; all of these stations are located in the main basin of Hamilton Harbour, with the exception of 370, near the mouth of Windermere Arm. TSS concentrations for surface-integrated samples were most variable at



stations 367, 268 and 370, and for bottom grab samples, most variable at stations 367, 369 and 268. TSS concentrations for surface-integrated samples were least variable at stations 352, 365 and 366, and for bottom grab samples, least variable at stations 370, 352, 365, and 366. Unlike total PCB concentration trends, the stations with the highest and lowest temporal variability for TSS were not grouped in one area of the Harbour. This finding suggests differences in temporal dynamics between PCB and TSS concentrations in the Harbour and that TSS concentrations are not a good proxy for tracking PCB concentration dynamics and trends in the Harbour. Further, inconsistencies between the relative temporal variability in TSS and PCB concentrations suggest that resuspension of in situ sediment is not an ongoing primary driver of PCB concentration trends at a given station; however, it does not eliminate the possibility of episodic resuspension.

No overall seasonal trends in total PCB concentration were apparent in the dataset driving the observed temporal variability (Figure 28), suggesting temporal variability in total PCB concentration observed was driven by episodic events rather than ongoing, more long-term processes occurring over the monitoring season. In contrast, there appeared to be a seasonal trend in PCB congener signature for surface-integrated samples from stations 258, 365, 367 and 368, all stations located in the main basin of the Harbour. For these stations and sample type (and bottom grab sample for station 367 as well), the proportion of less-chlorinated congeners appeared to increase throughout the monitoring season, with noticeably higher proportions during the August 19 and September 18 monitoring events (Figure 27).

Station 258

0

1

2

3

4

5

6

7

8

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)

Bottom grab sampleSurface-integrated sample

Station 268

0

20

40

60

80

100

120

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)




Station 352

05

101520253035404550

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)

Bottom grab sampleSurface-integrated sample Station 365

0

1

2

3

4

5

6

7

8

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)


Station 366

050

100150200250300350400450

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)


Station 367

0

1

2

3

4

5

6

7

8

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)


Station 368

0

1

2

3

4

5

6

7

8

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)

Bottom grab sampleSurface-integrated sample Station 369

0

20

40

60

80

100

120

140

160

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)




Station 370

0

5

10

15

20

25

30

35

May 28

, 200

8

June

11, 2

008

June

25, 2

008

July

9, 20

08

July

23, 2

008

Augus

t 6, 2

008

Augus

t 20,

2008

Septem

ber 3

, 200

8

Septem

ber 1

7, 20

08

Tota

l PC

B c

once

ntra

tion

(ng/

L)


Figure 28: Temporal trends of PCB concentrations at each station monitored during 2008 Notes: Total PCB concentrations were calculated using maximum or upper limit total PCB concentrations (congeners < detection assumed equal to detection). For stations located in the main basin of the Harbour, the same total PCB concentration scale was used whereas scale differs for stations located in Windermere Arm.

The significance and driver of increasing proportions of less-chlorinated congeners throughout the season remains unknown but suggests a relatively large role for a process other than resuspension in Harbour PCB dynamics. The driver is unlikely resuspension as the phenomenon is observed primarily in the upper water column away from the sediment water interface, and the congeners of interest have higher solubility and are thus less likely to be primarily found in the particle-phase. The seasonal trend in PCB congener signatures in stations located in the main basin of the Harbour could be reflecting an ongoing contribution of less-chlorinated congeners to the Harbour, which appear to be well mixed throughout the main basin of the Harbour and may build in significance over the season due to stratification and lack of mixing between the epilimnion and hypolimnion. Other possibilities include seasonal trends in fate and transport mechanisms in the Harbour (e.g. atmospheric inputs, fugacity, volatilization, etc.), which may not be as noticeable in the Windermere Arm stations due to dominance of other factors.

Further emphasizing the complex nature of PCB dynamics in Windermere Arm is that Harbour stations with high temporal variability in total PCB concentrations relative to TSS concentrations – stations 268, 352, 366, 369, and 370 – were all located in Windermere Arm. These five stations also had the highest total PCB concentrations measured during the 2008 survey (Figure 23), suggesting potential Harbour-wide implications in drivers of temporal variability.

The high variability in total PCB concentrations of surface-integrated samples at stations 366, 268 and 370 suggest episodic PCB inputs to the upper portion of the water column, that is, a source other than resuspension of bottom sediments. Further, these



three stations as well as station 352 all demonstrated temporal variability in PCB congener signature for the surface-integrated samples (and also bottom grab samples for stations 268 and 366; Figure 27). A noticeably higher proportion of less-chlorinated congeners was observed during the August 19 survey at these four stations further supporting the supposition of the influence of an external PCB source; the August 19 survey followed a relatively large rain event (Appendix I: May – September 2008 weather conditions in Hamilton). The high variability in total PCB concentrations of bottom grab samples at stations 366, 369 and 352 however, suggests episodic PCB inputs at depth, i.e. resuspension of contaminated bottom sediments. Relatively high TSS variability in bottom grab samples at station 369 further support the occurrence of resuspension at this location.

Thus, PCB dynamics are complex in Windermere Arm and several processes may be occurring simultaneously that result in elevated PCB concentrations in this portion of the Harbour. Windermere Basin may be a PCB source to the upper water column at station 268, resuspension may be a PCB source at station 369, and station 366 may be subject to both a PCB source to the upper water column as well as resuspension of surface sediment. Stations 352 and 370 may be integrating the impacts from the other nearby stations, but 352 may also be subject to in-situ sediment resuspension. A very interesting observation is that mean surface-integrated PCB concentrations were highest at station 369 of all stations monitored (Figure 23) but variability was low (Table 13), suggesting a consistent and strong PCB source to the upper portion of the water column at this station, as opposed to station 366 which may have more episodic inputs of PCBs at the surface. Stations 268, 366 and 369 integrate inputs from combined sewer overflows (CSOs) – the Parkdale, Strathearne and Kenilworth CSOs, respectively. Further investigation of PCB concentrations in these CSOs is recommended as a follow-up action to determine if CSO inputs are a driver of elevated PCB concentrations at these stations. Overall, data suggest episodic inputs of PCBs to Windermere Arm, which are likely acting as a source area to the main basin of the Harbour, where PCB concentrations varied little between surveys and PCB concentrations appear relatively well mixed.

3.2.8 Spatial Variability of PCB Water Concentrations in the Harbour Although water samples were primarily collected for examining the role of PCB fate and transport processes such as resuspension at each station, results were also used in conjunction with SPMD results towards investigating spatial variability in PCB concentrations throughout the Harbour that might indicate the potential presence of an active, locally-controllable PCB source. To test for significant differences in total PCB concentrations between stations, the non-parametric Kruskal-Wallis test was used instead of analysis of variance (ANOVA) as data were not assumed to be normally distributed and have similar variances between stations, particularly due to outliers



observed during the August 19 survey. Kruskal-Wallis tests conducted for both surface-integrated and bottom grab samples demonstrated that total PCB concentrations measured during the five independent surveys in 2008 from the nine stations sampled were not drawn from the same population; at least one of the nine stations for both sample types had significantly different total PCB concentrations (sample type 12: H = 38.11, p=0.000007; sample type 11: H=36.91, p=0.000012). As the null hypothesis of no difference between station medians was rejected by the results of the Kruskal-Wallis test, Mann-Whitney pairwise comparisons were computed for both sample type datasets (Table 14). For both sample types, there were no significant differences between stations 258, 365, 367 and 368, all stations located in the main basin of Hamilton Harbour. Groupings for samples collected from Windermere Arm stations were different for surface-integrated samples relative to bottom grab samples (Table 15), but generally show no significant difference in total PCB concentration among most stations located in Windermere Arm Table 14: Mann-Whitney pairwise comparison uncorrected (upper right) and Bonferroni corrected (lower left) p-values for a) Surface-integrated samples and b) Bottom grab samples. a) 258 268 352 365 366 367 368 369 370

258 0.01219 0.01219 0.6761 0.01219 0.9168 0.2506 0.01219 0.01219268 0.4387 0.4034 0.01219 0.09469 0.01219 0.01219 0.02157 0.09469352 0.4387 1 0.01219 0.0601 0.01219 0.01219 0.01219 0.09469365 1 0.4387 0.4387 0.01219 0.6761 0.1437 0.01219 0.01219366 0.4387 1 1 0.4387 0.01219 0.01219 0.1437 0.02157367 1 0.4387 0.4387 1 0.4387 0.8345 0.01219 0.02157368 1 0.4387 0.4387 1 0.4387 1 0.01219 0.01219369 0.4387 0.7766 0.4387 0.4387 1 0.4387 0.4387 0.01219370 0.4387 1 1 0.4387 0.7766 0.7766 0.4387 0.4387

b) 258 268 352 365 366 367 368 369 370

258 0.01219 0.01219 0.6761 0.01219 0.2101 0.8345 0.01219 0.03671268 0.4387 0.4034 0.01219 0.4034 0.01219 0.01219 0.4034 0.01219352 0.4387 1 0.01219 0.09469 0.01219 0.01219 0.09469 0.0601365 1 0.4387 0.4387 0.01219 1 0.4034 0.01219 0.01219366 0.4387 1 1 0.4387 0.01219 0.01219 1 0.01219367 1 0.4387 0.4387 1 0.4387 1 0.01219 0.01219368 1 0.4387 0.4387 1 0.4387 1 0.01219 0.01219369 0.4387 1 1 0.4387 1 0.4387 0.4387 0.01219370 1 0.4387 1 0.4387 0.4387 0.4387 0.4387 0.4387

Notes: p-values less than 0.05 are shown in yellow highlight. Statistical test performed in PAST (Hammer et al., 2001).



Table 15: Stations between which no significant difference in total PCB concentrations was determined according to the Mann-Whitney pairwise comparisons Station Surface-integrated

sample Bottom grab sample

258 365, 367, 368 365, 367, 368 268 352, 366, 370 352, 366, 369 352 268, 366, 370 268, 366, 369, 370 365 258, 367, 368 258, 367, 368 366 268, 352, 369 268, 352, 369 367 258, 365, 368 258, 365, 368 368 258, 365, 367 258, 365, 367 369 366 268, 352, 366 370 268, 352 352

In general, PCB concentrations in water showed a strong spatial gradient with increasing concentrations from the main basin of the Harbour, to Windermere Arm, to the ArcelorMittal Dofasco and Strathearne Avenue Slips. PCB water concentrations were approximately five fold higher in Windermere Arm (~20 ng/L) relative to the main basin of the Harbour (~4 ng/L), and in the ArcelorMittal Dofasco and Strathearne Ave Slips (~100 ng/L) another five fold higher than concentrations in Windermere Arm.

In addition to variability in total PCB concentrations among stations, variability in PCB congener profiles was also evident among stations during each event. While PCB congener profiles of water samples collected in the main basin of the Harbour appeared similar, there were noticeable differences in PCB congener profiles among stations in Windermere Arm and also between Windermere Arm stations and those located within the main basin of the Harbour (Figure 27). The PCB congener profile for stations 258, 365, 367, and 368 were similar, showing a similarity to a profile consisting of Aroclors 1254g, 1260 and 1242. For the most part, a similar PCB congener signature was also observed at stations 268, 352, and 370 except during the August 19 survey when a relatively higher proportion of less-chlorinated congeners was observed, possibly due to a higher contribution of Aroclor 1242. PCB congener signatures at stations 366 and 369 were each unique, with the former demonstrating an enrichment in less-chlorinated congeners and the latter demonstrating an enrichment in more-chlorinated congeners, likely due to higher proportions of Aroclors 1242 and 1260, respectively. While there were several obvious differences in PCB congener signatures among stations, the relative differences among stations differed according to the survey. For example, PCB congener profiles from May 28 appeared to have less variation among stations relative to profiles from the August 19 survey, suggesting spatial variability should be examined separately for each survey. To better examine spatial variability in PCB congener profiles, principle component analysis (PCA) was conducted for all water samples collected during each survey; results are presented in Figure 29.



May 28, 2008

372(11)372(12)367(11)367(12)365(11)365(12)258(11)

258(12)368(11)368(12)268(11)268(11)268(12)268(12)

366(11)366(12)

352(11)352(12)369(11)

369(12) 370(11)370(12)

A1260

-8 -6 -4 -2 2 4 6 8

Component 1

-9.6

-8

-6.4

-4.8

-3.2

-1.6

1.6

3.2

4.8

Com

pone

nt 2

PC1 has eigenvalue of 65; % variance is 64; PC2 has eigenvalue of 22 and % variance of 22.

372(11)372(12)367(11)367(12)365(11)365(12)258(11)258(12)368(11)368(12)268(11)268(11)268(12)268(12)

366(11)366(12)

352(11)352(12)369(11)369(12)370(11)370(12)

A1016

A1242

A1248aA1248g

A1254a

A1254g

A1260

-8 -4 4 8 12 16 20 24

Component 1

-9

-6

-3

3

6

9

12

15

18

Com

pone

nt 2



June 3, 2008

368(11)

368(12)367(11)

367(12)367(11)

367(12)365(11)

365(12)

258(11)

258(12)

369(11)

369(12)

352(11)

352(12)

366(11)366(12)

268(11)

268(12)

370(11)

370(12)

-4.8 -3.2 -1.6 1.6 3.2 4.8 6.4 8 9.6

Component 1

-2

-1.5

-1

-0.5

0.5

1

1.5

2

2.5

Com

pone

nt 2


368(11)368(12)367(11)367(12)367(11)367(12)365(11)365(12)258(11)258(12)

369(11)369(12)352(11)352(12)366(11)366(12) 268(11)268(12)370(11)

370(12)

A1016

A1242

A1248aA1248g

A1254a

A1254g

A1260

-28 -24 -20 -16 -12 -8 -4 4

Component 1

-18

-15

-12

-9

-6

-3

3

6

Com

pone

nt 2



June 30, 2008

368(11)

368(12)

258(11)

258(12)

367(11)367(12)

365(12)

365(11)

370(11)

370(12)

352(11)352(12)

352(11)

352(12)

268(11)268(12)

366(11)

366(12)

369(11)369(12)

-4.8 -3.2 -1.6 1.6 3.2 4.8 6.4 8 9.6

Component 1

-3

-2.4

-1.8

-1.2

-0.6

0.6

1.2

1.8

2.4

Com

pone

nt 2


368(11)368(12)258(11)258(12)367(11)367(12)365(12)365(11)370(11)

370(12)352(11)352(12)352(11)352(12)268(11)268(12)

366(11)366(12)

369(11)369(12)

A1016

A1242

A1248aA1248g

A1254a

A1254g

A1260

-30 -25 -20 -15 -10 -5 5 10 15

Component 1

-18

-15

-12

-9

-6

-3

3

6

Com

pone

nt 2



August 19, 2008

370(12)

370(11) 268(12)

268(11)352(12)

352(11)

368(12)368(11)

367(11)

367(12)367(12)

367(11)365(12)

365(11)

258(12)

258(11)

369(12)369(11)

366(12)

366(11)

-15 -12 -9 -6 -3 3 6 9

Component 1

-4.8

-4.2

-3.6

-3

-2.4

-1.8

-1.2

-0.6

0.6

Com

pone

nt 2


370(12)370(11) 268(12)268(11)352(12)352(11) 368(12)368(11)367(11)

367(12)367(12)367(11)365(12)365(11)258(12)258(11)

369(12)369(11)

366(12)366(11)

A1016

A1242

A1248aA1248g

A1254a

A1254g

A1260

-20 -16 -12 -8 -4 4 8 12 16

Component 1

-9

-6

-3

3

6

9

12

15

18

Com

pone

nt 2



September 18, 2008

258(11)258(12)

368(11)368(12)

367(12)367(11)

365(12)365(11)

370(12)370(11)352(12)

352(11)268(12)268(11)

366(11)

366(12)366(12)

366(11)

369(11)

369(12)

-15 -12.5 -10 -7.5 -5 -2.5 2.5 5

Component 1

-4

-3.2

-2.4

-1.6

-0.8

0.8

1.6

2.4

3.2

Com

pone

nt 2

PC1 has eigenvalue of 61; % variance is 59; PC2 has eigenvalue of 26 and % variance of 25. Figure 29: Principle Component Analysis (PCA) plots for water samples collected during each survey in 2008 relative to Aroclor mixtures. Notes: PCA was conducted on PCB signatures standardized to PCB congener % of total so samples could be compared against standard Aroclor signatures. PCA run in PAST.exe (Hammer et al., 2001). Aroclor profiles from US EPA (2006).

258(11) 258(12)368(11)368(12)

367(12)367(11)365(12)365(11)

370(12)370(11)352(12)352(11)268(12)268(11)

366(11)366(12)366(12)

366(11)

369(11)369(12)

A1016

A1242

A1248aA1248g

A1254a

A1254g

A1260

-20 -16 -12 -8 -4 4 8 12 16

Component 1

-9

-6

-3

3

6

9

12

15

18

Com

pone

nt 2



Results of the PCA are consistent with visual inspection of PCB congener profiles (Figure 27). For the May 28 and September 18 survey, most stations cluster together with the exception of stations 366, 372 (May 28 only) and 369. The station(s) in Strathearne Avenue Slip show(s) a stronger similarity to Aroclors 1242 and 1248a and 1248g, while the station in the ArcelorMittal Dofasco boat Slip shows a stronger similarity to Aroclor 1260. For the June 3 and June 30 surveys, again stations 366 and 369 cluster away from the other stations due to stronger similarities to less- and more-chlorinated Aroclors, respectively. However, station 352 (both sample types) and the surface-integrated sample of station 370 (June 3 survey) cluster relatively close to station 369, suggesting similarity in PCB source between these stations located in relative close proximity in Windermere Arm. The PCA plot for the August 19 survey is different again; while the two sample types for station 369 cluster even farther from most of the other stations, both sample types from station 268, and surface-integrated samples from stations 352 and 370 cluster close to station 366, suggesting similarity in PCB source between these stations all located in Windermere Arm.

Spatial variability data analyses suggest that any follow-up on further understanding PCB fate and transport mechanisms in the Harbour should be focused on Windermere Arm, where differences in spatial trends both for total PCB concentrations and PCB congener signatures are more pronounced relative to the main basin of the Harbour. There was more spatial differentiation for surface-integrated samples relative to bottom grab samples, suggesting much of the spatial variability is due to processes occurring in the upper water column.

3.2.9 Examination of PCB Anomalies and Potential PCB Sources in the Harbour Previous sections examined temporal and spatial variabilities in the Harbour and identified a PCB anomaly in Strathearne Ave Slip both in terms of elevated PCB concentrations and signature. To gain further insight into drivers and potential implications of this anomaly, PCB homolog profiles were examined as use of homologs improves comparison of PCB profiles between media due to different sets of congeners analyzed between water and sediment (Appendix II: MOE Analytical Methods). PCB homolog profiles for water samples from station 366 were compared to homolog profiles from station 366 sediment and final effluent from the Woodward Ave WWTP (Figure 30). The homolog profiles demonstrate a difference in signature between the bottom grab and surface-integrated samples, and that major changes in signatures between surveys is evident. While the homolog profiles from the June 30



and September 18 surveys show a similarity to the sediment profile, the homolog profile from the August 19 survey shows a similarity to the Woodward Ave WWTP homolog profile. The surface-integrated samples from May 28 and June 3 also show some similarity to the Woodward Ave WWTP homolog profile due to the enrichment of tri-chlorinated biphenyls. Homolog profiles are consistent with previous analyses suggesting two potential sources of PCBs in the Slip - both sediment resuspension and an external source.

Station 366 - May 28, 2008

0

5

10

15

20

25

30

35

40

Mono Di Tri Tetra Penta Hexa Hepta Octa Nona Deca

PCB

hom

olog

ue %

of t

otal

Sample type 11Sample type 12

Station 366 - June 3, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal



0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal


Station 366 - August 19, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal


Station 366 - September 18, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal

Sample type 11Sample type 12 Station 366 - Sediment

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal



Woodward Ave WWTP - average of 2007 data

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal

Aroclors

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal

A1016A1242A1248aA1248gA1254aA1254gA1260

Figure 30: PCB homolog profiles for station 366 water, station 366 sediment, and final effluent from the Woodward Ave WWTP relative to Aroclor profiles Notes: September 18 homolog profile is average of two replicates for both sample types 11 and 12. Sediment profile based on sediment sample collected August 19, 2008 at station 366 (see Section 3.6 Sediment Sampling in the Strathearne Avenue Slip) and Woodward Ave WWTP profile based on final effluent water samples collected during 2007 (Labencki, 2009). Aroclor profiles from US EPA (2006). The similarity of PCB profiles between a station in Strathearne Avenue Slip and the Woodward Ave WWTP was not expected given that the WWTP discharges to Red Hill Creek; however, the comparison was originally attempted due to a lack of PCB data for water from the Strathearne Ave CSO. In response to this finding, PCB congener profiles for station 366 as well as station 268 - the station downstream from the Woodward Ave WWTP - were compared to the PCB congener profile for final effluent from the Woodward Ave WWTP. A strong similarity in PCB congener signature in water was evident between these three locations, especially for the August 19 survey (Figure 31). Also, even more so than station 366, the homolog profile for station 268 on August 19 was quite distinct relative to the other surveys in that a high proportion of tri-chlorinated biphenyls were observed (Figure 32). Interesting to note is that the homolog profile differs from that measured in 1984, although caution must be used in interpretation as analytical methods have changed since the 1980s and the sample may not be representative of more long-term conditions in the water column at station 268. Nonetheless, the PCB congener pattern at stations 268 and 366 more closely resemble that from the Woodward Ave WWTP relative to Aroclor patterns, providing another line-of-evidence of the link between PCBs in Harbour water and that from the Hamilton sewer system.




0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28 (1)

May 28 (2)

Jun 3

Jun 30

Aug 19

Sep 18


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28 (1)

May 28 (2)

Jun 3

Jun 30

Aug 19

Sep 18


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28

Jun 3

Jun 30

Aug 19

Sep 18 (1)

Sep 18 (2)


0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

May 28

Jun 3

Jun 30

Aug 19

Sep 18 (1)

Sep 18 (2)

Woodward Ave WWTP - average of 2007 data

0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

Aroclor mixtures

0

2

4

6

8

10

12

14

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

A1016 A1242 A1248a

A1248g A1254a A1254g

A1260



0

2

4

6

8

10

12

141

4+10 8 16 19

28+3

3 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

Aug 19 stn 366 (surface-integrated sample)Aug 19 stn 268 (surface-integrated sample)Ave 2007 Woodward Ave WWTP dataA1242

Figure 31: PCB congener profiles for water samples from station 268, station 366, and the Woodward Ave WWTP relative to Aroclor profiles. Notes: Woodward Ave WWTP profile based on final effluent water samples collected during 2007 (Labencki, 2008). Aroclor profiles from US EPA (2006).

Station 268 - Homolog Pattern in Water Sampled May 28, 2008

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal

Bottom grab (Average)

Surface depth-integrated(Average)

Station 268 - Homolog Pattern in Water Sampled June 3, 2008

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal

Bottom grabSurface depth-integrated



Station 268 - Homolog Pattern in Water Sampled June 30, 2008

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal


Station 268 - Homolog Pattern in Water Sampled August 19, 2008

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal


Station 268 -

Homolog Pattern in Water Sampled September 18, 2008

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal


Homolog Pattern in Water Sampled in 1984 Near Station 268 (Mudroch et al., 1989)

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal

Station 1 (north)Station 2 (south)

Figure 32: PCB homolog profiles for water samples collected from station 268 in 2008 relative to 1984 Notes: Homolog profile for water sampled in 1984 from Mudroch et al. (1989). Samples from 1984 were collected from the middle of the water column with a Van Dorn Bottle. The similarity in PCB congener profiles for water samples collected at stations 366 and 268 suggests a common source, that is, the Woodward Ave WWTP; however, water monitoring in 2007 did not find anomalous total PCB concentrations from the plant (Labencki, 2009) and the plant does not discharge to the Strathearne Avenue Slip. Reasons for the similarity in PCB profiles between these locations are not known, although a potential explanation is contribution of PCBs routed through the CSO system. Stations 268 and 366 are located close to CSO discharge locations, namely the Parkdale and Strathearne Ave CSOs, respectively. While the Woodward Ave WWTP routinely receives waters from the combined sewer system, following large precipitation events, stormwater that is typically routed to the Woodward Ave WWTP may overflow to discharge points such as the Parkdale and Strathearne Ave CSOs.

Additionally, the PCB signature at all three locations has high proportions of PCB congeners 4+10, 18, 28+33 and 31. While high proportions of these congeners may be evidence of Aroclors 1016 and/or 1242, these technical Aroclor mixtures also have a



high proportion of PCB congener 8, which is generally not present in the water samples from the Harbour. Thus, the PCB congener signature from stations 268 and 366 and the Woodward Ave WWTP may have some alteration from a pure technical Aroclor mixture as reported in the literature. As discussed for the 2007 water monitoring results from the Woodward Ave WWTP, the unique PCB signature which has high proportions of less-chlorinated congeners may be due to dechlorination or alteration of a primary PCB source. Also important to note in this context is that when less-chlorinated congeners are detected, they are likely to have been more recently generated due to their higher tendency to volatilize (NYAS, 2005, p.66). Follow-up of this anomaly and evaluation of a potential PCB source in the area should be pursued through future PCB congener analysis of waters collected from CSOs which discharge to the southeast corner of the Harbour. The unique PCB signature enriched in less-chlorinated congeners present at station 366, at station 268 during the August 19 survey and at the Woodward Ave WWTP is also observed at other locations in the Harbour, albeit at lower proportions. Although the PCB homolog profiles for water collected from station 352 shows a similarity to in situ sediment and a higher proportion of more-chlorinated congeners in bottom grab samples suggesting PCB sediment suspension, anomalously high proportions of tri-chlorinated biphenyls were observed during the August 19 survey (Figure 33), likely due to the same phenomenon which impacted stations 268 and 366. Inspection of the PCB congener profile for station 352 (Figure 27) shows the unique signature with high proportions of congeners 4+10, 18, 28+33 and 31, also seen at stations 268 and 366.

Station 352 - May 28, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal

Sample type 11Sample type 12 Station 352 - June 3, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal





0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal

Sample type 11Sample type 12 Station 352 - August 19, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal



0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal


Station 352 - Sediment

0

5

10

15

20

25

30

35

40


PCB

Hom

olog

ue %

of t

otal

Figure 33: PCB homolog profiles for water and sediment samples collected from station 352 Notes: June 30 homologue profile is average of two replicates for both sample types 11 and 12. Sediment profile based on sediment sample collected December 11, 2003 at station 352 (Labencki, 2008). Observation of the unique PCB signature seemingly sourced from stations 268 and 366 in ambient Harbour waters is not restricted to Windermere Arm. Although the PCB homolog profile for water samples collected from station 258 show a similarity to in situ sediment through high proportions of hexa-chlorinated biphenyls, homolog profiles also demonstrate potential influence from Windermere Arm sources (Figure 34). Relatively higher proportions of tri-chlorinated biphenyls were observed in the surface-integrated samples, especially during the August 19 and September 18 surveys; examination of the PCB congener profiles again demonstrates high proportions of congeners 4+10, 18, 28+33 and 31 (Figure 27). In fact, a spatial gradient of tri-chlorinated biphenyls is observed during the August 19 survey with decreasing proportions from station 366 water samples (~38%), to surface-integrated samples at station 352 (~28%) to surface-integrated samples at station 258 (~19%).

Further to this, increasingly higher proportions of tri-chlorinated biphenyls were



observed at centre station throughout the five surveys, suggesting a gradual build-up of the congeners of note in upper waters of the Harbour, likely due to input to the epilimnion during stratification. This finding is consistent with that observed during the 2007 field season at station 258, when proportions of less-chlorinated biphenyls in depth-integrated water samples increased from the April, to May to July 2007 surveys (Labencki, 2009). Interesting to note however, is that the temporal pattern in tri-chlorinated biphenyls at station 352 does not seem to follow the same seasonal trend; station 352 may be reflecting more of what is occurring closer to the source. Thus, follow-up on the source of the unique PCB signature is important as it may be influencing Hamilton Harbour at large, especially considering that less-chlorinated PCBs have higher potential for biotic uptake through pelagic exposure due to higher water solubility of these congeners, an implication explored further in the next chapter examining results of semi-permeable membrane device (SPMD) deployments in the Harbour (3.3.5 Implications of 2008 SPMD and Water Sampling).

Station 258 - May 28, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal

Sample type 11Sample type 12 Station 258 - June 3, 2008

0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal



0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal



0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal





0

5

10

15

20

25

30

35

40


PCB

hom

olog

ue %

of t

otal


Station 258 - Sediment

0

5

10

15

20

25

30

35

40


PCB

Hom

olog

ue %

of t

otal

Figure 34: PCB homolog profiles for water and sediment samples collected from station 258 Notes: Sediment profile based on sediment sample collected August 10, 2006 at station 258 (MOE database - EMRB Index Station monitoring).



3.3 Semi-Permeable Membrane Device (SPMD) Deployment in Hamilton Harbour Semi-permeable membrane devices (SPMDs) were deployed in Hamilton Harbour to identify any spatial anomalies in PCB concentration which might be indicative of an active, locally-controllable source of PCBs. While results of water sampling also provide a line-of-evidence in such an investigation, water samples are limited in source trackdown as they only provide data for an instantaneous moment in time, and may not be representative of more long-term or typical conditions at each station. In this regard, PCB concentration results from SPMDs are advantageous as they provide an indication of conditions over the entire duration of deployment, representing both quiescent conditions and events. Nonetheless, water sampling results provide environmentally-relevant PCB concentrations and information on the potential role of resuspension and other fate and transport processes of PCBs in Hamilton Harbour. Results from both water sampling and SPMD deployment work were used in tandem to identify potential PCB source areas in the Harbour. Additional theoretical information on the use of SPMDs is described in Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods.

3.3.1 Quality Assurance/Quality Control (QA/QC) of SPMD Deployments

Three SPMD replicates were deployed per station as a means of increasing confidence in results through acting as a check on sample variability. As a quantitative measure of variability, the coefficient of variation (CV)8 was calculated for each replicate set (Table 16), with a CV of zero signifying no difference between replicate samples. For the summer 2008 SPMD dataset, CVs ranged from 0.06 (Station 369; deployment 2) to 0.48 (Station 366; deployment 2) and had an overall median CV of 0.17 suggesting moderate variability between replicates, with some stations demonstrating particularly high variability between replicates during one of the deployment periods (e.g. Station 268 - deployment 1 (CV = 0.45); Station 366 - deployment 2 (CV = 0.48)). While the reason for the variability between replicates is not known, the high variability for these stations does not impinge on interpretation of most results due to the overall high total PCB concentrations measured in all replicate SPMDs from these stations.

8 Coefficient of variation = standard deviation / mean



Table 16: Total PCB concentrations (ng/mL triolein or ng/SPMD) in all SPMDs deployed in Hamilton Harbour during 2008. Deployment 1 – June 2008 Deployment 2 – August 2008 Stn

Rep 1 Rep 2 Rep 3 Mean Standard deviation

CV Rep 1 Rep 2 Rep 3 Mean Standard deviation

CV Summer 2008 mean

258 85.85a 226.50 283.89 255.19 40.58 0.16 lost 625.98 433.82 529.90 135.87 0.26 392.55 268 1,762.01 1,904.24 706.76 1,457.67 654.18 0.45 2,823.47 2,246.58 3,320.25 2,796.77 537.33 0.19 2,127.22 352 1,651.56b 1,569.27b 2,102.58 1,774.47 287.12 0.16 2,221.20 1,508.97 2,603.10 2,111.09 555.31 0.26 1,942.78 365 323.07 362.01 311.19 332.09 26.58 0.08 487.44 378.28 698.56 521.42 162.82 0.31 426.76 366 11,068.66 9,809.91 12,898.30 11,258.96 1,552.97 0.14 9,263.24 12,785.57 22,997.86 15,015.56 7133.69 0.48 13,137.26 367 393.87 262.09 375.06 343.67 71.27 0.21 429.78 435.39 351.43 405.53 46.94 0.12 374.60 368 562.42 351.67 374.84 429.64 115.97 0.27 407.38 359.70 422.37 396.48 32.73 0.08 413.06 369 3,107.19 3,831.43 3,696.69 3,545.10 385.18 0.11 5,304.76 4,770.63 4,912.23 4,995.87 276.72 0.06 4,270.49 370 1071.26 700.21 808.30 859.92 190.83 0.22 2,107.95 1,545.04 1,929.80 1,860.93 287.70 0.15 1,360.43 371 175.97 145.31 175.26 165.52 17.50 0.11 117.25 165.62 154.54 145.80 25.34 0.17 155.66 Notes: a – due to low recovery of the internal standard and lower total PCB concentration relative to replicates 2 and 3, replicate 1 was removed from the dataset for calculation of Station 258 (June) average results. It was suggested that biofouling may have prevented a better extraction of this SPMD replicate. Blue-green algae can affect SPMD results as it clogs polyethylene; this is why an internal standard is used (T. Metcalfe, 2008, pers. comm.). b – Total PCB concentration may be underestimated as congeners 28, 31 and 33 could not be quantified for these replicates.



In order to gauge potential contamination of SPMD samples, both lab blanks and field blanks were included as part of the SPMD QA/QC analysis. Three lab blanks were analyzed per deployment set of SPMDs, for a total of six lab blanks for the entire summer 2008 SPMD sample set. Five of the six SPMD lab blanks had PCB concentrations of “0”, and one had a PCB concentration of 5.77 ng/mL triolein, all relatively low PCB concentrations for the sample set and not indicative of laboratory sample contamination.

The PCB concentrations in the SPMD field blanks were generally low; 60% of field blanks had no detectable PCB concentrations (“0”) and 95% of field blanks had PCB concentrations between 0 and 4.07 ng/mL triolein (Table 17). Despite the relatively low PCB concentrations in most field blanks, an anomalously high PCB concentration was measured at the Station 370 field blank during deployment 2 (50.10 ng/mL triolein). While this concentration is high in an absolute sense, it only represents approximately 2.7% of the average sample PCB concentration for this station and deployment and thus, potential contamination is not likely having a large influence on results interpretation. Sample SPMDs were not blank-corrected. Table 17: Total PCB concentrations (ng/mL triolein or ng/SPMD) in SPMD field blanks Station Deployment 1

(June 2008) Deployment 2 (August 2008)

258 1.70 0 268 1.38 0.53 352 2.80 3.59 365 0 0 366 0 4.07 367 0 2.37 368 0 0 369 0 0 370 0 50.10 371 0 0

The reasons for the contamination of the Station 370 SPMD field blank during deployment 2 is unknown; however, it is reasonable to assume that this field blank may have come into contact with a sample SPMD. Contamination of the station 370 (August) field blank may not necessarily have come from station 370 sample SPMDs however, as the PCB congener profiles between the paired sample and field blank SPMD are not similar (Figure 35)9. The enrichment of more-chlorinated PCB congeners in the station 370 field blank SPMD suggests that the contamination was not likely 9 PCB congener profiles of SPMD field blanks from other stations were not examined due to overall low total PCB concentrations in these samples, and no field/lab contamination suspected.



airborne. While it may be a coincidence, it is noted that during deployment 2, station 370 was the first retrieval conducted on September 17, similar to the scenario that occurred with the water sampling field blank on September 18, when potential contamination occurred at station 258, the first station sampled on that particular day (3.2.1 Quality Assurance/Quality Control of Water Samples).

0

2

4

6

8

10

12

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al

Stn 370 (Aug) Field blankStn 370 (Aug) Sample rep 1Stn 370 (Aug) Sample rep 2Stn 370 (Aug) Sample rep 375% 1254 + 25% 1260

Figure 35: PCB congener profile for the August 2008 Station 370 field blank relative to Station 370 samples and an Aroclor profile. Notes: Aroclor profiles from US EPA (2006).

Although not directly related to the PCB results, the condition of the metal shrouds and the external surface of the SPMDs upon retrieval were noted for each deployment period (Appendix V: Qualitative field notes on condition of metal shrouds and external surface of SPMDs upon retrieval). These qualitative field observations imply a great deal about the general water quality at the station of note during the 28-day deployment period, e.g. oxygen regime, presence of algae, etc. and could possibly have some bearing on the outcome of the SPMD results; however, these observations are generally outside the scope of the SPMD results and therefore not further discussed in this report. Continuous temperature measurements taken at the depth at which SPMDs were deployed in the water column (Table 4) were recorded at each station with the use of Tidbits. These data were collected to aid in SPMD interpretation as the ambient temperature of the water column can influence PCB uptake into SPMDs whereby higher PCB uptake rates into SPMDs are predicted at higher temperatures (Rantalainen et al.,



2000). Despite the positive correlation between temperature and uptake rates, for temperature to be a major explanatory factor for differences in PCB concentrations among SPMDs of differing ambient temperature regimes, relatively large differences in temperature are needed; sampling rates of SPMDs were only found to be higher by a factor of three at 30 °C relative to rates at 2 °C (Booij et al., 2003). Raw temperature data from each station for both deployment periods are available in Appendix VI: Tidbit Temperature Data for Ten Stations and Two SPMD Deployments. The mean temperatures were similar among stations during each deployment period (Figure 36). During deployment 1, the minimum mean temperature was at station 367 (17.10 °C) and the maximum mean temperature was at station 371 (23.19 °C) for a range of 6.09 °C among station means. During deployment 2, the minimum mean temperature was again at station 367 (20.89 °C) and the maximum mean temperature was at station 369 (23.99 °C) for a range of 3.1 °C among station means. The mean deployment temperature for all stations were on average 2.3 °C higher during deployment 2 relative to deployment 1 (range: ΔT 1.17 °C at station 370; ΔT 3.93 °C at station 369). Generally, the temperature differences among stations and deployment periods were relatively small suggesting similar SPMD sampling rates among stations and deployment periods. Thus temperature likely did not play a large role in resulting PCB concentrations in SPMDs, especially considering the order-of-magnitude differences in PCB concentrations among stations (Table 16).

0

5

10

15

20

25

30

258 268 352 365 366 367 368 369 370 371

Mea

n Te

mpe

ratu

re (C

)

Deployment 1 - June 2008Deployment 2 - August 2008

Figure 36: Mean water temperature (°C) at depth of SPMD deployment at each station during each of the two deployment periods. Notes: Error bars represent one standard deviation of the temperature data for each deployment period. There are no temperature data for station 371 for the second deployment period as the Tidbit had technical difficulties and data were not able to be retrieved from the device.



3.3.2 Total PCB Concentrations in SPMDs

For the two deployments conducted during summer 2008, total (replicate mean) PCB concentrations varied by deployment period and among stations. Total mean PCB concentrations in SPMDs ranged over two orders-of-magnitude throughout the Harbour during summer 2008; the minimum and maximum PCB concentrations were 145.80 ng/mL triolein at Station 371 (deployment 2) and 15,015.56 ng/mL triolein at Station 366 (deployment 2), respectively (Table 16; Figure 37). The mean PCB concentration in SPMDs for both deployments also followed this spatial trend as the summer 2008 mean concentration was lowest at station 371 (155.66 ng/mL triolein) and highest at station 366 (13,137.26 ng/mL triolein). PCB concentrations in SPMDs from station 258 during 2008 (255 ng/mL triolein – deployment 1; 530 ng/mL triolein – deployment 2) were similar in magnitude to MOE Index Station Monitoring10 results for this station monitored in June-July 2006 (308 ng/mL triolein) and September 2006 (675 ng/mL triolein) suggesting inter-annual consistency in ambient PCB concentrations in the Harbour.

0

2000

4000

6000

8000

10000

12000

14000

16000

258 268 352 365 366 367 368 369 370 371

ng/m

L tr

iole

in

Average June ResultsAverage August Results

Figure 37: PCB concentrations in SPMDs deployed in Hamilton Harbour during 2008. Notes: Solid bars represent average concentration of three replicates, except for station 258 which was an average of two replicates for both June and August results. Error bars represent plus and minus one standard deviation of replicate samples.

10 The Index Station Monitoring Program is the MOE’s ambient nearshore lake monitoring program; stations are sampled every 3 years in lakes Ontario and Erie, and every 6 years in lakes Huron and Superior.



There are no provincial or federal guidelines for PCB concentrations in SPMDs, so as a point of reference and for additional context on results, summer 2008 SPMD PCB concentrations from Hamilton Harbour were compared to results obtained from other MOE SPMD deployments across Ontario (Figure 38). For the 2006 Lake Ontario Index Station Monitoring, PCB concentrations in SPMDs deployed at six stations ranged from 7 ng/mL triolein at Humber Bay (station 06 01 2047) to 308 ng/mL triolein at Hamilton Harbour (station 09 01 258). The second highest PCB concentration in the 2006 dataset however, was 46 ng/mL triolein from Toronto Inner Harbour (station 06 01 1364), approximately an order-of-magnitude lower than the Hamilton Harbour concentration. For the 2007 Lake Erie Index Station Monitoring, PCB concentrations in SPMDs deployed at five stations ranged from 5 ng/mL triolein at Port Stanley (station 16 01 0658) to 274 ng/mL triolein at West Basin Lake Erie (station 16 01 370). Thus, PCB concentrations in SPMDs are approximately an order-of-magnitude higher at Hamilton Harbour centre station (station 258) and two to three orders-of-magnitude higher in the Strathearne Avenue Slip (station 366) relative to ambient lake concentrations. PCB concentrations in SPMDs deployed in Cootes Paradise while high in comparison to ambient lake conditions, were consistently lower than concentrations in the Harbour and are thus not suggestive of a local PCB source.

1

10

100

1000

10000

100000

1364

Tor

onto

Har

bour

*

2047

Hum

ber B

ay

3777

Nia

gara

Bar

258

Ham

ilton

Har

bour

9712

New

cast

le

462

Tren

ton

210

Upp

er L

. St.

Cla

ir

209

Eas

t L. S

t. C

lair

370

Wes

t Bas

in L

. Erie

658

Off

Por

t Sta

nley

656

Off

Gra

nd R

iver

371

367

365

258

368

370

352

369

268

366PC

B c

once

ntra

tion

(ng/

mL

trio

lein

)

2006 Lake Ontario index station data

2007 Lake Erie index station data

Hamilton Harbour main basin

stations (2008)

Hamilton Harbour Windermere Arm stations (2008)

Figure 38: PCB concentrations in SPMDs deployed in Hamilton Harbour during 2008 relative to PCB concentrations measured at other nearshore locations in the lower Great Lakes during 2006 and 2007. Notes: Logarithmic scale on y-axis. *Concentration for station 1364 (Toronto Inner Harbour) is an average of September 2005 and June – July 2006 results; all other Lake Ontario and Lake Erie index station data are one month deployments from June – July, 2006, and June – July, 2007, respectively. Hamilton Harbour 2008 SPMD data represent the average of all replicates from both deployments.



SPMDs have also been used extensively by the MOE to locate active, locally-controllable sources of PCBs in Project Trackdown. Prior to investigations, PCB Trackdown sites were identified for inclusion in the program due to anomalously high PCB concentrations in ambient media (e.g. water, sediment, fish). Thus, such areas represent some of the more highly-contaminated PCB hotspots across the province that have been located and subsequently been subject to remediation projects.

During the course of multiple investigations in three separate Trackdown areas (12 Mile Creek, Etobicoke Creek, Turkey Creek), the highest PCB concentration in SPMDs recorded in the Trackdown program was 4,865 ng/mL triolein in 12 Mile Creek during the 2003-04 investigation (Figure 39). PCB concentrations of this magnitude were also measured in SPMDs deployed in Etobicoke Creek during 2002 (3,780 ng/mL triolein) and 2005 (3,447 ng/mL triolein). The high concentrations of PCBs in the 12 Mile Creek SPMDs were primarily due to PCB-contaminated sediment and soils, where PCB concentrations exceeded hazardous waste limits (50 ppm) and were up to 3,000,000 ng/g (or 3000 ppm) (N. Benoit, 2009, pers. comm.).

0

2000

4000

6000

8000

10000

12000

14000

371

367

365

258

368

370

352

369

268

366

12 M

ile C

reek

(200

3-04

) max

Eto

bico

ke C

reek

(200

2) m

ax

Eto

bico

ke C

reek

(200

5) m

ax

Turk

ey/L

ittle

Cre

ek(2

004)

max

Turk

ey C

reek

(200

5) m

ax

PCB

con

cent

ratio

n (n

g/m

L tr

iole

in)

Trackdown maximum PCB concentrations

Hamilton Harbour main basin

stations (2008)

Hamilton Harbour Windermere Arm stations (2008)

Figure 39: Mean PCB concentrations in SPMDs deployed in Hamilton Harbour during 2008 relative to maximum PCB concentrations in SPMDs from Project Trackdown.



The Trackdown Project results provide context for Hamilton Harbour as the PCB concentrations in SPMDs deployed at most of the Windermere Arm stations during 2008 were on par with those measured at PCB Trackdown sites, and PCB concentrations in SPMDs deployed in the Strathearne Ave Slip were approximately a factor of three higher than the highest PCB concentration measured in the Trackdown program. Further emphasizing the severity of the elevated PCB concentrations in the Hamilton Harbour 2008 SPMD results, particularly those from the Strathearne Avenue Slip (station 366), PCB concentrations in SPMDs from station 366 are the highest that scientists at Trent University have analyzed to-date (T. Metcalfe, 2009, pers. comm.). PCB concentrations in SPMDs deployed in Windermere Arm, and Strathearne Ave Slip in particular, are suggestive of a local PCB source.

3.3.3 Temporal Variability in PCB SPMD Concentrations The temporal variability of PCB concentrations between the June and August SPMD deployments were examined to determine the general consistency in PCB source at each station, although important to note is that the primary purpose of SPMD deployment was investigation of spatial trends. Average PCB concentrations in SPMDs at eight of the ten stations were higher during the August deployment relative to the June deployment; only stations 368 and 371 had higher concentrations in June relative to the August deployment, albeit the difference in average concentrations between deployments was small. Temporal variability was highest at stations 370, 258 and 268 where PCB concentrations in SPMDs were approximately two fold higher in August relative to June, and temporal variability was lowest at stations 368, 371, 352, and 367 where concentrations were relatively the same between the June and August deployments (Table 18). Table 18: Temporal variability of PCB concentrations in SPMDs as measured as a ratio of the two deployments during summer 2008 Station 258 268 352 365 366 367 368 369 370 371 Ratioa 2.1 1.9 1.2 1.6 1.3 1.2 1.1b 1.4 2.2 1.1b Notes: a - Ratio = [Mean PCB] of deployment with higher mean [PCB] / [Mean PCB] of deployment with lower mean [PCB] b - Ratio was calculated as replicate average August/June concentration, except for stations 368 and 371 where June/August ratio was calculated due to lower concentrations in August relative to June. Temporal variability of the PCB concentrations in SPMDs were compared to the temporal variability of PCB concentrations in water samples to aid in interpretation of the 2008 dataset. High temporal variability was observed at stations 370 and 268 for both SPMD and water sampling (sample type 12) datasets; however, high temporal variability in PCB concentrations from station 258 SPMDs contrasts to relatively low temporal variability in total PCB concentrations in water samples from this station. Reasons for this are not known, however, important to note is that station 258 only had



2 replicates for both SPMD deployments relative to 3 replicates analyzed for all other stations. Another contrast between temporal variability of SPMDs and water samples was for station 352; while PCB concentrations in SPMDs had low temporal variability, relatively high temporal variability was observed for bottom grab water samples at this site. Again, reasons for this are not known.

The differences between the lists of stations with high (or low) temporal variability when cross-referencing between SPMD and water sampling results may be due to conditions or events which occur between water sampling surveys. Such events would not be represented in water sampling results which only reflect conditions during an instantaneous moment in time. Of particular note is the difference in magnitude in temporal variability between SPMD and water sampling results for station 366 – while mean PCB concentrations in SPMDs increased only by a factor of 1.3 from the June to August deployment periods (Table 18), PCB concentrations in water samples varied over an order-of-magnitude between sampling occasions (Table 13). While these results suggest the potential for sporadic events of highly elevated PCB concentrations in the Strathearne Avenue Slip, a caveat to the SPMD data from this station is the high variability between replicate samples, especially during the second deployment (Table 16). PCB concentrations in SPMDs can become elevated either due to consistently high PCB concentrations in the water column, or periodic spikes of very high PCB concentrations in the water column, the latter of which appears to be more consistent with the 2008 water sampling results at station 366. Also of interest is the finding of potential seasonality in SPMD PCB concentrations; higher PCB concentrations in SPMDs were measured during August relative to the June deployment period at eight of the ten stations. Higher PCB concentrations in SPMDs during the late summer relative to the early summer was also observed during 2006 Index Station monitoring for SPMD deployments at station 258 (Figure 40). One possible driver for the increase in PCB concentration through the summer is higher average water temperatures in August relative to June which act to increase PCB uptake rates in SPMDs, however, the mean temperatures for all stations were on average only 2.3 °C higher during the August deployment period relative to June (3.3.1 Quality Assurance/Quality Control (QA/QC) of SPMD Deployments). This increase in temperature is not likely large enough to be the primary driver for the PCB concentration increase between deployment periods. Booij et al. (2003) noted that PCB uptake by SPMDs was approximately three-fold higher at 30 °C relative to 2 °C, a 28 °C increase in temperature. As the increase in PCB uptake in Hamilton Harbour was similar in magnitude (approximately a two-fold increase between June and August), the increase in uptake was thus not likely due to a relatively small (2.3 °C) increase in temperature. In fact, the smallest mean temperature change between deployment periods was at station 370 (Figure 36), the same station which had the largest relative increase in PCB concentrations between deployment periods (Table 18), suggesting the increased PCB uptake in August is not likely due to temperature induced effects.



0

100

200

300

400

500

600

700

800

2006 2008

PCB

con

cent

ratio

n (n

g/m

L tr

iole

in)

June/JulyAugust/September

Figure 40: PCB concentrations in SPMDs deployed at station 258 in 2006 and 2008. An alternative hypothesis for higher PCB uptake in August relative to the June SPMD deployment period is higher flows during August relative to June as Booij et al. (2003) found that water flow velocity has a large impact on SPMD sampling rates. Although actual Harbour flows during June and August 2008 are not known, precipitation patterns and total amounts during each deployment period were examined as a proxy for potential in-Harbour flows. Although the total amount of precipitation that fell during each deployment period was similar (93.4 mm – deployment 1; 103.1 mm – deployment 2; Environment Canada, 2008a), the distribution pattern of precipitation events was quite different between June and August 2008 (Figure 41). One large difference between the deployment periods was that for deployment 1, most rain fell during the first half of the deployment period, whereas for deployment 2, most rain fell during the second half of the deployment period. It is unknown how or if this precipitation pattern would impact PCB uptake by deployed SPMDs.



0

5

10

15

20

25

30

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29

Day of SPMD deployment

Prec

ipita

tion

(mm

)

Deployment 1 - 93.4 mmDeployment 2 - 103.1 mm

Figure 41: Daily precipitation measured in Hamilton during both SPMD deployment periods during summer 2008. Notes: data from Environment Canada (2008a)

Another hypothesis for higher PCB uptake by SPMDs in August relative to the June deployment period is higher concentrations of PCBs in the water column during August relative to June. The water monitoring results however do not support an overall increase in total water column PCB concentration between the June and August/September sampling events, albeit only five surveys were conducted during the 2008 season and are not likely representative of seasonal or long-term trends in the Harbour. There was no overall trend as to the survey of when the maximum total PCB water column concentration was measured at each station, although no station maximum concentration was measured on June 3, 2008 and only station 368 (sample type 12) had a maximum concentration measured on June 30, 2008. All other maximum PCB concentrations in water at each station were measured on May 28, August 19 or September 18, 2008 (Table 8).

Finally, an additional hypothesis for higher PCB uptake in August relative to June is a change in PCB congener profiles between these survey periods. An increase in the proportion of less-chlorinated congeners from April to July 2007 (Labencki, 2009) and May through September 2008 was found for water samples from Station 258 (Section 3.2.9 Examination of PCB Anomalies and Potential PCB Sources in the Harbour).



Similarly, higher proportions of less-chlorinated congeners were observed in SPMDs during the August deployment relative to the June deployment at stations 258, 365, 367 and 368, all stations in the main basin of the Harbour; somewhat higher proportions were observed at stations 268 and 370 and temporal patterns were not readily discernable at other stations (Figure 42).

Station 258

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al

258 rep 1 (June)258 rep 2 (June)258 rep 1 (Aug)258 rep 2 (Aug)

Station 268

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al

268 rep 1 (June)268 rep 2 (June)268 rep 3 (June)268 rep 1 (Aug)268 rep 2 (Aug)268 rep 3 (Aug)

Station 352

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al


Station 365

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al


Station 366

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al


Station 367

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al

367 rep 1 (June)367 rep 2 (June)367 rep 3 (June)367 rep 1 (June)367 rep 2 (June)367 rep 3 (June)



Station 368

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al


Station 369

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al


Station 370

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al


Station 371

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al


Aroclors

0

2

4

6

8

10

12

14

16

18

20

17 18 28 31 33 44 49 52 70 74 95 99 101

105

110

118

128

132

138

149

151

153

170

180

187

191

194

195

201

205

206

208

209

PCB

con

gene

r % o

f tot

al

A1016A1242A1248aA1248gA1254aA1254gA1260

Figure 42: PCB congener patterns for all replicate SPMDs deployed at each station during two deployment periods Notes: Aroclor profiles from US EPA (2006).

Less-chlorinated congeners more readily accumulate in SPMDs relative to more-chlorinated congeners as the polyethylene bag of a SPMD only samples dissolved-phase PCBs (Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods), which is the phase less-chlorinated congeners are more likely to be found in due to a higher solubility in water relative to more-chlorinated congeners which



more readily bind to particles in the water column. Therefore, because total PCB concentrations have low variability in the water column throughout the season in the main basin of the Harbour (3.2.7 Temporal Variability in PCB and TSS Concentrations) but there is a higher proportion of less-chlorinated congeners in August relative to June, total PCB concentrations measured in SPMDs in such areas would expected to be higher during the August deployment. Due to this mechanism, it is challenging to distinguish between variable source contributions (i.e. episodic loadings) and varying PCB congener signatures as a driver for variable total PCB concentrations in SPMDs, and hence, determining the relative consistency in source at each station. Such would also be the case for comparing between two stations with similar total PCB concentration but very different PCB congener signatures. While the change in PCB congener signature as a potential driver to varying total PCB concentrations in SPMDs is worth noting, so are potential drivers for this change in PCB congener signature between deployment periods. The shift toward higher proportions of less-chlorinated congeners in SPMDs deployed at stations in the main basin of the Harbour during the second deployment period is consistent with results of the water sampling (3.2.7 Temporal Variability in PCB and TSS Concentrations). As hypothesized for the seasonal trend in PCB congener signatures for water samples collected from stations located in the main basin of the Harbour, this trend may be reflecting an ongoing contribution of less-chlorinated congeners to the Harbour which may build in significance possibly due to inputs primarily to the epilimnion and lack of whole Harbour mixing due to summer stratification. Water samples from station 366 and from station 268, particularly during the August 19, 2008 survey were enriched in tri-chlorinated biphenyls, suggesting that intermittent inputs and PCB dynamics in Windermere Arm may be impacting the entire Harbour both in terms of absolute PCB concentration and PCB signature.

3.3.4 Spatial Variability in Total PCB Concentrations in SPMDs

The two SPMD deployments in Hamilton Harbour during 2008 were primarily intended to investigate spatial variability in PCB concentrations throughout the Harbour which might be indicative of the presence of an active, locally-controllable source of PCBs. To test for significant differences in total PCB concentrations in SPMDs between stations, the non-parametric Kruskal-Wallis test was used instead of analysis of variance (ANOVA) as data were not assumed to be normally distributed and have similar variances between stations. The Kruskal-Wallis test performed on total PCB concentrations for each replicate sample grouped by station demonstrated that PCB concentrations measured during the two deployments in 2008 from the ten stations sampled were not drawn from the same population; at least one of the ten stations had significantly different total PCB concentrations (H = 52.74, p= 0.000000033).



As the null hypothesis of no difference in total PCB concentrations in SPMD replicates among stations was rejected by the results of the Kruskal-Wallis test, Mann-Whitney pairwise comparisons were computed for all PCB replicate SPMD samples (Table 19). Station 371 - which had the lowest PCB concentrations in SPMDs during 2008 (Table 16) – was significantly different than all other stations except for station 258 (Table 20). Identical to the results of the Mann-Whitney test for water samples (Table 14), there were no significant differences in total PCB concentrations among SPMDs deployed at stations 258, 365, 367 and 368, all stations located in the main basin of the Harbour. Similar to the spatial trend observed for water samples (3.2.8 Spatial Variability of PCB Water Concentrations in the Harbour), there was no significant difference among PCB concentrations in SPMDs deployed at stations 268, 352 and 370, all located in Windermere Arm. A spatial trend not observed in the water sampling results however, is that both stations 366 and 369, the stations with the two highest PCB concentrations in SPMDs during 2008 (Figure 37) each had significantly different PCB concentrations in SPMDs compared to all other stations in the Harbour. Table 19: Mann-Whitney pairwise comparison uncorrected (upper right) and Bonferroni corrected (lower left) p-values for total PCB concentrations in SPMD replicate samples.

258 268 352 365 366 367 368 369 370 371258 0 0.008113 0.008113 0.3153 0.008113 0.6481 0.5228 0.008113 0.008113 0.1207268 0.3651 0 0.4712 0.005075 0.005075 0.005075 0.005075 0.008239 0.1735 0.005075352 0.3651 1 0 0.005075 0.005075 0.005075 0.005075 0.005075 0.1282 0.005075365 1 0.2284 0.2284 0 0.005075 0.9362 0.8102 0.005075 0.005075 0.005075366 0.3651 0.2284 0.2284 0.2284 0 0.005075 0.005075 0.005075 0.005075 0.005075367 1 0.2284 0.2284 1 0.2284 0 0.8102 0.005075 0.005075 0.005075368 1 0.2284 0.2284 1 0.2284 1 0 0.005075 0.005075 0.005075369 0.3651 0.3708 0.2284 0.2284 0.2284 0.2284 0.2284 0 0.005075 0.005075370 0.3651 1 1 0.2284 0.2284 0.2284 0.2284 0.2284 0 0.005075371 1 0.2284 0.2284 0.2284 0.2284 0.2284 0.2284 0.2284 0.2284 0

Notes: p-values less than 0.05 are shown in yellow highlight. Statistical test performed in PAST (Hammer et al., 2001). Table 20: Stations between which no significant difference in total PCB concentrations in replicate SPMDs was determined according to the Mann-Whitney pairwise comparisons

Station Stations with which station of note has no significant difference 258 365, 367, 368, 371 268 352, 370 352 268, 370 365 258, 367, 368 366 Significantly different than all other stations 367 258, 365, 368 368 258, 365, 367 369 Significantly different than all other stations



370 268, 352 371 258

In general, PCB concentrations in SPMDs showed a strong spatial gradient with increasing concentrations from Cootes Paradise, to the main basin of the Harbour, to Windermere Arm, to the ArcelorMittal Dofasco Boat Slip, to the Strathearne Avenue Slip (Figure 37). PCB concentrations in SPMDs were approximately five fold higher in Windermere Arm (~1,900 ng/mL triolein) relative to the main basin of the Harbour (~400 ng/mL triolein), and PCB concentrations in the ArcelorMittal Dofasco Boat Slip were approximately two fold higher than the concentrations in Windermere Arm. PCB concentrations in SPMDs deployed in the Strathearne Avenue Slip however, were approximately seven fold higher than concentrations in Windermere Arm, and well over a magnitude higher than concentrations in the main basin of the Harbour. As noted previously, the spatial gradients observed for SPMDs are similar to the results observed for water sampling (3.2.8 Spatial Variability of PCB Water Concentrations in the Harbour), except that stations 366 and 369 each have PCB concentrations in SPMDs statistically different than all other Windermere Arm stations, unlike that observed for water sampling. Also, the relative difference between mean PCB concentrations among station groupings (i.e. spatial variability) was different for SPMDs relative to water sampling results. While PCB concentrations in water increased approximately five fold from the main basin of the Harbour to Windermere Arm similar to SPMDs, PCB concentrations in water increased another five fold from Windermere Arm to the ArcelorMittal Dofasco and Strathearne Ave Slips, which is greater than the relative increase for SPMDs in the ArcelorMittal Dofasco Boat Slip (two fold increase relative to Windermere Arm) and less than the relative increase for SPMDs in the Strathearne Ave Slip (seven fold increase relative to Windermere Arm).

The differences in spatial trends between total PCB concentrations in water and SPMD samples may be due to PCB dynamics occurring in the water column at the Slips not captured by water sampling which only reflects an instantaneous snapshot of conditions at the time of sampling. The very high PCB concentrations in SPMDs in Windermere Arm stations, especially the Strathearne Ave Slip, suggests episodic PCB contributions to the water column; this finding is consistent with high temporal variability found for water samples from stations 366, 268 and 370 (suface-integrated samples) and stations 366, 369 and 352 (bottom grab samples) (3.2.7 Temporal Variability in PCB and TSS Concentrations). The very high PCB concentrations in SPMDs also suggest that peak PCB water concentrations following these episodic contributions likely exceed PCB concentrations measured during the 2008 surveys (Table 8), especially considering the relatively lower PCB concentrations in SPMDs deployed at PCB Trackdown locations (Figure 39)

Another potential explanation for the much larger difference in PCB



concentrations between SPMDs deployed at stations 366 and 369 relative to the total concentrations observed in the water samples is a difference in PCB congener profile between these Slips. As mentioned previously, a PCB profile with a high proportion of less-chlorinated congeners (i.e. station 366) may be resulting in a higher total accumulation of PCBs in SPMDs relative to a station that has a PCB profile with a higher proportion of more-chlorinated congeners (i.e. 369), due to the higher solubility of less-chlorinated congeners and SPMDs only sampling the dissolved-phase (Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods). An important caveat to this however is that total water concentrations may not be representative of ongoing conditions at the stations due to episodic contributions, and it is hard to distinguish between effects due to differences in PCB congener signature relative to episodic contributions not captured in instantaneous water sampling.

In addition to variability in total PCB concentrations among stations, variability in PCB congener profiles was also evident among stations during each SPMD deployment. While there were several obvious differences in PCB congener signatures among stations, the relative differences among stations differed somewhat according to the deployment. To better examine spatial variability in PCB congener profiles, principle component analysis (PCA) was conducted for each SPMD deployment (Figure 43) and used in conjunction with the PCB congener profiles (Figure 42) to help identify any potential anomalies and provide more information in results interpretation. An in-depth comparison of SPMD PCB profiles to Aroclor profiles was not done for SPMDs as profiles in SPMDs are a product of only the dissolved phase PCBs present in the water column, and may not be representative of all PCBs present.



Deployment 1 – June 2008

258-rep1(June)258-rep2(June)268-rep1(June)268-rep2(June)268-rep3(June)

352-rep1(June)

352-rep2(June)

352-rep3(June)

365-rep1(June)365-rep2(June)365-rep3(June)

366-rep1(June)366-rep2(Jun

366-rep3(June)367-rep1(June)



368-rep3(June)

369-rep1(June)

369-rep2(June)

369-rep3(June)



A1016

A1242A1248aA1248g

A1254a

A1254g

A1260

-12 -8 -4 4 8 12 16 20

Component 1

-7.5

-5

-2.5

2.5

5

7.5

10

12.5

Com

pone

nt 2



366-rep3(June)

12 12.6 13.2 13.8 14.4 15 15.6 16.2 16.8 17.4

Component 1

Com

pone

nt 2

PC1 has eigenvalue of 72.6; % variance is 48; PC2 has eigenvalue of 31.9 and % variance of 20.9.


352-rep1(June)

352-rep2(June)

352-rep3(June

365-rep1(June)365-rep2(June)365-rep3(June)367-rep1(June)

367-rep2(June) 367-rep3(June)

368-rep1(June)


369-rep1(June)

369-rep2(June)

369-rep3(June)



-6.4 -4.8 -3.2 -1.6 1.6 3.2 4.8

Component 1

-6.4

-4.8

-3.2

-1.6

1.6

3.2

4.8

6.4

Com

pone

nt 2



Deployment 2 – August – September 2008

258-rep1(Aug)258-rep2(Aug)

268-rep1(Aug)268-rep2(Aug)268-rep3(Aug)

352-rep1(Aug)

352-rep2(Aug)


365-rep2(Aug)

365-rep3(Aug)

366-rep1(Aug)366-rep2(Aug)366-rep3(Aug)

367-rep1(Aug)367-rep2(Aug)367-rep3(Aug)368-rep1(Aug)

368-rep2(Aug)

368-rep3(Aug)

369-rep1(Aug)


370-rep1(Aug)


371-rep1(Aug)


A1016A1242

A1248aA1248g

A1254a

A1254g

A1260

-16 -12 -8 -4 4 8 12 16

Component 1

-15

-12.5

-10

-7.5

-5

-2.5

2.5

5

7.5

Com

pone

nt 2

258-rep1(Aug)

258-rep2(Aug)

352-rep3(Aug)

365-rep1(Aug)

365-rep2(Aug)

365-rep3(Aug)

366-rep1(Aug) 366-rep2(Aug)

366-rep3(Aug)


367-rep3(Aug)

368-rep1(Aug)

368-rep2(Aug)

368-rep3(Aug)

370-rep1(Aug)

370-rep2(Aug)

370-rep3(Aug)

371-rep1(Aug)

371-rep2(Aug)

371-rep3(Aug)-7.5 -5 -2.5 2.5 5 7.5 10

Component 1

-0.8

0.8

1.6

2.4

3.2

4

4.8

5.6

Com

pone

nt 2

PC1 has eigenvalue of 77.6; % variance is 46.8; PC2 has eigenvalue of 28.8 and % variance of 17.3. Figure 43: Principle Component Analysis (PCA) plots for SPMDs during each deployment in 2008 relative to Aroclor mixtures. Notes: PCA was conducted on PCB signatures standardized to PCB congener % of total so samples could be compared against standard Aroclor signatures. PCA run in PAST.exe (Hammer et al., 2001). Aroclor profiles from US EPA (2006).



The PCB congener profile from station 371 clustered close to stations in the main basin of the Harbour during deployment 1, and for deployment 2, clustered further from these stations but with Replicate 1 from station 370 and Replicate 3 from station 366. Important to note however is that there were differences in the profiles between replicate samples, especially during the second deployment which confounds interpretation. Nonethelesss, a local anomaly in PCB congener signature is not evident for this station in Cootes Paradise.

Although the PCB profile differed between deployments, PCB congener profiles of SPMDs deployed at stations 258, 365, 367 and 368, all in the main basin of the Harbour, clustered together for both deployments demonstrating a strong similarity in PCB profile among these stations (Figure 42), similar to the spatial pattern of PCB congener profiles for water samples from these stations (3.2.8 Spatial Variability of PCB Water Concentrations in the Harbour). The profile is characterized by a mix of both less- and more-chlorinated congeners, with a higher proportion of less-chlorinated congeners during the second deployment, also similar to the water sampling results. Also like the water sampling results, there were differences in SPMD PCB congener profiles among stations in Windermere Arm and also between Windermere Arm stations and those located within the main basin of the Harbour (Figure 42). The PCB profiles for SPMDs deployed at stations in Windermere Arm however, were not as temporally consistent as stations in the main basin of the Harbour and also demonstrated some differences relative to the spatial patterns observed for water sampling results. For both deployments, station 370 clustered close to the stations in the main basin of the harbour demonstrating some similarity, although Replicate 1 from the August deployment demonstrated a different profile which may be QA/QC related (3.3.1 Quality Assurance/Quality Control (QA/QC) of SPMD Deployments) so should be interpreted with caution. Also for both deployments, station 352 demonstrated variability in PCB profile between replicates making interpretation challenging as each of the three replicates clustered with different stations. For deployment 1, the station 352 replicate 1 was most similar to the profiles from the main basin of the Harbour, while replicate 2 was most similar to the profile from station 369 and replicate 3 was most similar to the cluster formed by stations 268 and 366. For deployment 2, the station 352 replicates 1 and 2 were unique and did not cluster close to other stations, while replicate 3 clustered with stations from the main basin of the Harbour. While reason for this variability remains unknown, it may be that station 352 is influenced by numerous PCB sources in the Harbour. Stations 268 and 366 clustered together for deployment 1 separate from all other stations demonstrating a strong similarity in PCB profile between these stations and a signature unique from other stations. The PCB congener profiles (Figure 42) demonstrate an enrichment of less-chlorinated congeners at these stations for both



deployments, but the PCA plot for deployment 2 does not have a separate cluster for stations 268 and 366. While station 268 clusters away from the other stations for deployment 2, each of the three replicates for station 366 plots on a different area, with replicates 1 and 2 clustering near stations from the main basin of the Harbour and replicate 3 plotting near station 370 replicate 1 and station 371 replicates. High variability in total PCB concentration between replicates deployed during deployment 2 was noted as a potential QA/QC issue (3.3.1 Quality Assurance/Quality Control (QA/QC) of SPMD Deployments) so as such, the profiles obtained during deployment 2 for station 366 should be interpreted with caution. The same mechanism responsible for variability in total PCB concentration in the station 366 SPMDs may also play a role in the resulting PCB profile. The PCB profiles for station 369 clustered away from all other stations during both deployments, demonstrating a unique PCB signature at this station enriched in more-chlorinated congeners (Figure 42). The unique signature at station 369 as well as a similarity to Aroclor 1260 is consistent with water sampling results (3.2.8 Spatial Variability of PCB Water Concentrations in the Harbour). The strong contribution of A1260 to the PCB profiles in SPMDs from station 369 could be deciphered as the high proportion of the more-chlorinated congeners at this station could only be from this mixture, as no other Aroclor contains these congeners. An interesting difference between the water sampling and SPMD PCB congener profiles is that the similarity in PCB congener profiles among stations 268, 352 and 370 for water samples was not observed in SPMDs; there seemed to be different clustering among stations for PCB profiles in SPMDs relative to water samples. Additionally, a unique PCB profile was observed in Windermere Arm water samples during the August 19 survey that was enriched in less-chlorinated congeners (3.2.6 Variability of Total PCB Concentrations with Depth in the Water Column at Each Station). A PCB profile also enriched in less-chlorinated congeners, particularly tri-chlorinated biphenyls, was observed in SPMDs deployed at stations 366 and 268 for both deployments, suggesting that the driver of the PCB signature observed in water samples on August 19 may be an ongoing phenomenon at stations 268 and 366. As discussed previously, this input may be from the Parkdale and Strathearne Ave CSOs due to the similarity of the station 366 and 268 homolog profiles to effluent from the Woodward Ave WWTP (Figure 44).




0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal



0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal


Station 366 -

Homolog pattern in SPMDs deployed 2008

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal

JuneAugust

Station 268 - Homolog pattern in SPMDs deployed 2008

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal

JuneAugust

Woodward Ave WWTP -

Average Homolog Pattern of 2007 Water Sampling Data

0

10

20

30

40

50

60


PCB

hom

olog

ue %

of t

otal

Figure 44: Homolog patterns for water samples and SPMDs deployed at stations 268 and 366 relative to the homolog pattern for effluent from the Woodward Ave WWTP Notes: Homolog patterns for SPMDs represent the average of three replicates during each deployment period. Homolog pattern for Woodward Ave WWTP represents the average of final effluent water samples collected during 2007 (Labencki, 2009). Mono and di homologs not analyzed in SPMDs.



3.3.5 Implications of 2008 SPMD and Water Sampling

While it is generally understood that bioaccumulation and subsequent biomagnification of PCBs from diet is the major route of PCB exposure in aquatic environments (i.e. uptake of PCBs from contaminated sediment by benthos), PCBs can also be bioaccumulated directly from the water column through pelagic exposure. SPMDs are a proxy for biotic uptake through pelagic exposure at a site of interest as they sample PCBs only in the dissolved phase (Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods). Thus, a high PCB concentration in SPMDs, such as measured in Hamilton Harbour during 2008, also means high potential for pelagic PCB exposure to local biota. High PCB concentrations in local biota, likely in large part due to pelagic exposure, have been demonstrated in Hamilton Harbour through elevated PCB concentrations in young-of-the-year (YOY) fish (Figure 45; Labencki, 2008). YOY fish have a small home range, a basic known diet, and a known length of exposure, thus limiting potential explanatory factors when contaminant concentrations are elevated. The high PCB concentrations in both SPMDs and YOY fish relative to reference sites suggest that pelagic PCB exposure in Hamilton Harbour may be playing a larger role in bioaccumulation of PCBs to the local food web relative to other sites. YOY PCB Concentrations in Hamilton Harbour

0

200

400

600

800

1000

1200

1400

1991CCIW

1994CCIW

1999CCIW

2000CCIW

2003CCIW

2006CCIW

1991BGC

1999BYC

1991WC

2006GC

2006GC

Mea

n PC

B c

once

ntra

tion

(ng/

g w

w)

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0M

edia

n fis

h le

ngth

(cm

)

spottail shiner

emerald shiner



YOY PCB Concentrations in Western Lake Ontario

0

200

400

600

800

1000

1200

1400

2000Burlington

Beach

2003Burlington

Beach

2006Burlington

Beach

1997OakvilleHarbour

2000BronteCreek

2000MimicoCreekmouth

2000MimicoCreekmouth

2003 PortDalhousie

2003 PortDalhousie

Mea

n PC

B c

once

ntra

tion

(ng/

g w

w)

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

Med

ian

fish

leng

th (c

m)

spottail shiner

emerald shiner

Figure 45: PCB concentrations in YOY fish over time in Hamilton Harbour (upper; 5 locations) and Lake Ontario (lower) Notes: Figure from Labencki (2008). Bars represent mean PCB concentrations for each year/sampling location, and error bars represent +/- one standard deviation. There is no error bar for 2006 GC as bar represents results from one sample. Diamonds represent median fish length. Note that both Hamilton Harbour and Western Lake Ontario graphs are on the same scale. Locations in Hamilton Harbour are as follows: CCIW = South of Canada Centre for Inland Waters; BGC = Burlington Golf Course; BYC = Burlington Yacht Club; WC = Willow Cove; GC = Grindstone Creek. A potential reason for relatively high PCB uptake though pelagic exposure in Hamilton Harbour is the nature of the PCB congener profile, which has relatively high proportions of less-chlorinated congeners (3.2.9 Examination of PCB Anomalies and Potential PCB Sources in the Harbour). Less-chlorinated congeners have higher water solubility relative to more-chlorinated congeners, and thus total PCB concentrations composed of a high proportion of less-chlorinated congeners are more likely to have a higher proportion of PCBs in the dissolved-phase. Preferential uptake of less-chlorinated congeners by fish through pelagic exposure was demonstrated through a bioassay conducted in March 2004 with fathead minnows; the PCB congener profile in fish tissue was enriched in less-chlorinated congeners relative to paired PCB congener profile in sediment (Figure 46), likely due to both partitioning of less-chlorinated congeners to the water column from sediment as well as uptake kinetics, among other factors. Hence, the local food web may be more influenced by pelagic exposure in areas with high proportions of less-chlorinated congeners relative to areas where total PCB is primarily reflective of Aroclor 1254/1260.



Station WABA01 - March 2004

0123456789

10

PC

B018

PC

B028

PC

B037

PC

B049

PC

B054

PC

B074

PC

B087

PC

B099

PC

B105

PC

B114

PC

B119

PC

B126

PC

B138

PC

B151

PC

B155

PC

B157

PC

B168

PC

B171

PC

B178

PC

B183

PC

B188

PC

B194

PC

B201

PC

B205

PC

B208

PCB

con

gene

r % o

f tot

al

fishsediment


0

2

4

6

8

10

12

PC

B01

8

PC

B02

8

PC

B03

7

PC

B04

9

PC

B05

4

PC

B07

4

PC

B08

7

PC

B09

9

PC

B10

5

PC

B11

4

PC

B11

9

PC

B12

6

PC

B13

8

PC

B15

1

PC

B15

5

PC

B15

7

PC

B16

8

PC

B17

1

PC

B17

8

PC

B18

3

PC

B18

8

PC

B19

4

PC

B20

1

PC

B20

5

PC

B20

8

PCB

con

gene

r % o

f tot

al

fishsediment


0

2

4

6

8

10

12

PC

B018

PC

B028

PC

B037

PC

B049

PC

B054

PC

B074

PC

B087

PC

B099

PC

B105

PC

B114

PC

B119

PC

B126

PC

B138

PC

B151

PC

B155

PC

B157

PC

B168

PC

B171

PC

B178

PC

B183

PC

B188

PC

B194

PC

B201

PC

B205

PC

B208

PCB

con

gene

r % o

f tot

al

fishsediment


0

2

4

6

8

10

12

PC

B01

8

PC

B02

8

PC

B03

7

PC

B04

9

PC

B05

4

PC

B07

4

PC

B08

7

PC

B09

9

PC

B10

5

PC

B11

4

PC

B11

9

PC

B12

6

PC

B13

8

PC

B15

1

PC

B15

5

PC

B15

7

PC

B16

8

PC

B17

1

PC

B17

8

PC

B18

3

PC

B18

8

PC

B19

4

PC

B20

1

PC

B20

5

PC

B20

8

PCB

con

gene

r % o

f tot

al

fishsediment

Figure 46: PCB congener profiles of fathead minnow tissue from 3-week exposure bioassays conducted on surface sediment from Windermere Arm. Notes: Sediment from WABA01-WABA04 sampled December 2003 and bioassay conducted March 2004 at Laboratory Services Branch of the MOE. Fathead minnows were exposed to sediment for three weeks in an enclosed vessel. Stations WABA01-WABA03 are located in Windermere Arm, and station WABA04 is a reference station in western Hamilton Harbour (Labencki, 2008).

Although a number of different factors may be responsible for the elevated PCB concentrations in YOY fish sampled in 2006 and SPMDs in 2008 (e.g. pulses of high total PCB concentrations), the presence of relatively high proportions of less-chlorinated PCBs in Hamilton Harbour should be considered as a potential explanatory factor. Following this, the source of the less-chlorinated PCBs – Windermere Basin/Strathearne Slip – should also be flagged as potential source zones for any resulting elevated pelagic exposure. Implications of the presence of an enrichment of less-chlorinated PCBs in Hamilton Harbour are also extended to physical fate and transport processes and corresponding biological “source zones” in the Harbour relative to more-chlorinated PCBs, which are generally sediment-bound. In addition, the enrichment of less-chlorinated congeners towards the end of the summer as observed in both water and SPMDs may have additional implications in terms of timing of this phenomenon such as on the life history of fish, regardless of what is driving the late summer shift in PCB profile.



3.4 WWTP primary sludge sampling

Total PCB concentrations in primary sewage sludge sampled from Dundas, Woodward and Skyway WWTPs ranged from 72 ng/g dw (Skyway WWTP; June 26, 2008) to 370 ng/g dw (Woodward Ave WWTP; June 26, 2008) for the two surveys conducted during the 2008 season (Table 21). Although only two surveys were conducted, data demonstrated relatively low temporal variability and high consistency in relative PCB concentrations between the three WWTPs for the two surveys. The highest PCB concentration in sludge for each survey was measured from the Woodward Ave WWTP; PCB concentrations were approximately three to five times greater at this WWTP relative to concentrations from the Dundas and Skyway WWTPs. In addition, the relative sludge concentrations between Woodward Ave and Skyway WWTPs are consistent with relative final effluent concentrations measured in 2007 (Labencki, 2009); the median PCB concentration in final effluent from Woodward was approximately four times greater than that from Skyway, similar to the relative difference observed in the 2008 sludge concentrations. Table 21: Total PCB concentrations (ng/g dry weight) measured in primary sewage sludge from three WWTPs during two surveys in 2008. June 26, 2008 September 4,

2008 Mean of two

surveys Dundas WWTP 90 84 87 Woodward Ave WWTP 370 290 330 Skyway 72 85 78.5

The use of sewage sludge data as a general indicator of relative PCB contributions to and presence within the three main Harbour sewersheds suggests that PCB contributions to the waste stream in Dundas and Burlington are lower relative to that in Hamilton. Further, data suggest that the Woodward Ave WWTP sewershed is the primary PCB source area in the Hamilton Harbour AOC, assuming equal conveyance to the Harbour across sewersheds. This may in part be due to the large combined sewer system which contributes both sanitary sewage and stormwater to the Woodward Ave WWTP.

In addition, the sludge data are another line-of-evidence that high PCB concentrations measured at the Desjardins Canal in 2007 were likely reflecting Harbour water quality, rather than due to high concentration inputs from the local WWTP, a potential source of PCBs to Cootes Paradise. Assuming similar PCB removal efficiencies between Dundas WWTP and Skyway WWTP, which had similar PCB concentrations in sewage sludge in 2008, then the PCB concentration in final effluent



from the Dundas WWTP may be similar to that at Skyway WWTP, which was approximately 1 ng/L for 6 events monitored during 2007 (Labencki, 2009).

Although no PCB congener-specific analysis was conducted, for the June 26, 2008 samples, the lab noted that all three samples resembled a mixture of Aroclor 1248, 1254 and 1260; for September 4, 2008, the lab noted a similarity to Aroclors 1254 and 1260. The presence of these technical mixtures in sludge is not surprising given that all three mixtures consist of relatively high proportions of more-chlorinated PCB congeners which have a higher affinity to bind to particles, which subsequently settle out of the waste stream as sludge. This theoretical explanation is consistent with PCB congener signatures observed in the final effluent stream from the Woodward Ave WWTP in 2007 which had relatively high proportions of less-chlorinated congeners (Labencki, 2009). The change in PCB congener signature between influent (primary sludge - 2008) and final effluent (2007 – Labencki, 2009) may be due to dechlorination through the plant or differential removal of PCB congeners due to a gradient of physical-chemical properties reflective of the degree of biphenyl chlorination. Further interpretation of PCB congener signatures at the WWTPs is beyond the scope of this report and available dataset.



3.5 Event-based water sampling in Chedoke Creek Total (maximum) PCB concentrations in Chedoke Creek were <3.81 ng/L, <3.42 ng/L and <3.21 ng/L on May 8, June 16 and August 26, 2008, respectively; all data measured during these sampling events are shown in Table 22. During the May 8 event, field notes indicate that the Creek did not appear impacted by the rain event (D. Supper, 2008, pers. comm.), despite 9.2 mm of rain having fallen in the past 24 hours (Appendix I: May – September 2008 weather conditions in Hamilton). Rainfall measured at the Hamilton airport by Environment Canada on May 8, 2008 may have been localized in nature. During the June 16 event, the Creek flow was noticeably impacted and water levels were up by 0.5 m; field notes also indicated that the water samples appeared extremely turbid (D. Supper, 2008, pers. comm.). During the August 26 event (dry event), some small oil plumes were noted on the water surface and attempts were made to capture some of the slick in the water samples (D. Supper, 2008, pers. comm.). Despite the different water quality regimes and observations recorded during the three surveys, PCB concentrations varied very little between events.

In contrast, total suspended solids (TSS) concentrations varied by almost three fold between the events sampled as TSS concentrations were 20.7 mg/L, 47.9 mg/L and 18.1 mg/L on May 8, June 16 and August 26, 2008, respectively. Thus, PCB concentrations were not clearly correlated to TSS concentrations as PCB concentrations varied very little relative to the variability in TSS concentration. It should be noted however that only three events were sampled, and thus, sample size is small and may not be representative of long term trends. Mean total PCB concentrations measured in Chedoke Creek during 2008 were compared to mean total PCB concentrations measured in Red Hill Creek, Indian Creek, Grindstone Creek and in the Desjardins Canal during 2007 (Labencki, 2009). Although the 2008 mean total PCB concentration in Chedoke Creek (3.48 ng/L) was above the provincial water quality objective (PWQO) of 1 ng/L (MOEE, 1994), the mean concentration was similar in magnitude to concentrations that have been measured at other Hamilton Harbour tributaries (Figure 47). In addition, the total PCB concentrations were within the range of background concentrations for the Great Lakes, noted as 1-20 ng/L from one source (Strachan and Eisenreich, 1990 in Erickson, 1997) and <5 ng/L from another (WHO, 1976 in Erickson, 1997). Thus, the 2008 water monitoring data from Chedoke Creek do not suggest that there is a PCB anomaly in Chedoke Creek that warrants further follow-up action.



Table 22: Results of 2008 water sampling in Chedoke Creek, station 09 15 0010 Total PCB (ng/L) Date Event

type Conductivity,

ambient (UMHO/cm)

Dissolved Oxygen,

field (mg/L)

pH, field

Temperature, water, field

(°C) (minimum)1 (maximum)2

Particulate (mg/L)

May 8 Wet 761 10.9 8.05 13.2 3.71 <3.81 20.7 June 16

Wet 615 8.7 8.07 16.1 3.06 <3.42 47.9

August 26

Dry 1370 10.1 8.25 18.6 3.09 <3.21 18.1

1 - Minimum PCB concentrations were calculated assuming any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was equal to zero for purposes of calculating minimum total PCB concentration; this is a less conservative approach to estimating total PCB concentration from reported PCB congener concentrations. 2 - Maximum PCB concentrations represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration.



0

1

2

3

4

5

6

Red HillCreek -2007

IndianCreek -2007

GrindstoneCreek -2007

DesjardinsCanal -2007

ChedokeCreek -2008

Mea

n to

tal P

CB

con

cent

ratio

n (n

g/L)

Figure 47: Mean 2008 total PCB concentration in Chedoke Creek relative to mean 2007 total PCB concentration in other Hamilton Harbour tributaries (Labencki, 2009). Notes: Error bars represent plus and minus one standard deviation. Mean PCB concentrations are “maximum” PCB concentrations which represent an upper limit as any PCB congener reported by the lab as “actual result is less than the reported value” (i.e. less than detection) was assumed equal to its detection limit for purposes of calculating maximum total PCB concentration.

Data also suggest that the PCB concentrations observed in the Desjardins Canal in 2007 were likely influenced by Hamilton Harbour waters rather than Chedoke Creek as the mean 2008 Chedoke Creek PCB concentration was less than the mean PCB concentration observed in the Desjardins Canal in 2007, albeit not by much. It is important to note however, that the lower portion of Chedoke Creek has been undergoing remediation activities in recent years, including 2008 when bank construction was ongoing during the summer sampling period. Comparison of monitoring results between years must also be done with caution due to different meteorological conditions between years; for example, 2007 was a very dry year in the Hamilton area, and 2008 was a very wet year. The PCB congener patterns for the three Chedoke Creek surveys were also examined to determine variability between events and similarity to standard Aroclor



patterns (Figure 48). Generally, the PCB congener pattern was similar between events, although slightly higher proportions of more-chlorinated congeners were observed on the June 16, 2008 event relative to the other events. This small shift in PCB congener pattern is likely due to relatively higher TSS concentrations observed during this event (Table 22), as more-chlorinated congeners have a stronger affinity for bonding to particles. Also, there was high variability between events in the proportion of less-chlorinated congeners observed (< PCB 37), with a very high proportion of PCB 4+10 observed on August 26, 2008; reasons for this remain unknown.

0

2

4

6

8

10

12

14

14

+ 8 16 19 28 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129

137

141

151

155

157

169

171

177

180

187

189

194

200

202

205

207

209

PCB

con

gene

r % o

f tot

al

May 8June 16August 2640% A1016 + 30% A1254g + 30% A1260

Figure 48: PCB congener profiles for three 2008 Chedoke Creek surveys Notes: Aroclor profiles from US EPA (2006). Generally, the water samples from Chedoke Creek showed a strong similarity to Aroclors 1254g and 1260 (Figure 48). The Chedoke Creek PCB profiles also showed some similarity to Aroclor 1016, although due to the very high variability in proportions of less-chlorinated congeners between events, it is difficult to determine if the Chedoke Creek profiles are most like Aroclor 1016 relative to similar Aroclor 1242 or even Aroclor 1248 (Figure 49). The presence of less-chlorinated congeners may also be due to contribution from a non-Aroclor source, such as atmospheric deposition and/or weathering/dechlorination.



0

2

4

6

8

10

12

14

161

4+10 8 16 19

28+3

3 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

con

gene

r % o

f tot

alA1016A1242A1248aA1248gA1254aA1254gA1260

Figure 49: PCB congener patterns of seven Aroclors Notes: Aroclor profiles from US EPA (2006). As one of the reasons that water from Chedoke Creek was sampled in 2008 was due to uncertainty about the origin of elevated PCB concentrations in the Desjardins Canal observed in 2007 (1.1.3 Follow-up to determine source of PCBs measured at the Desjardins Canal), the PCB congener profile from Chedoke Creek was compared to the Desjardins Canal and Hamilton Harbour centre station congener patterns observed in 2007 (Figure 50). As the PCB congener pattern from the 2007 Desjardins Canal water samples appear to differ little from both the Chedoke Creek and Hamilton Harbour Centre Station water sample profiles, PCB congener patterns do not provide clear evidence on whether the elevated PCB concentration at the Desjardins Canal in 2007 was due to PCB inputs from Chedoke Creek or backwash from the Harbour. Further analysis through principal component analysis (PCA) also does not demonstrate a clear similarity between PCB congener patterns at the Desjardins Canal to Chedoke Creek or the Harbour (Figure 51), although the Desjardins Canal samples appear to cluster more strongly with the Harbour samples relative to the Chedoke Creek samples, except for the June 16, 2008 Chedoke Creek profile. For this event, the Chedoke Creek profile has a stronger similarity to the 2007 Desjardins Canal profiles relative to the other two events sampled in 2008 in the Creek. These results suggest that PCB concentrations at the Desjardins Canal may be more influenced by the Harbour on an ongoing basis,



but that Chedoke Creek may be a relatively stronger influence following wet events. Nonetheless, total PCB concentrations measured in Chedoke Creek in 2008 are not anomalous in nature (Figure 47) and thus follow-up action in Chedoke Creek is not warranted. Both the total PCB concentrations and PCB congener profiles in Chedoke Creek measured in 2008 suggest that Chedoke Creek was not the likely source of the relatively high PCB concentration measured at the Desjardins Canal in 2007; it remains likely that the Harbour was the source of PCBs at the Canal.

Chedoke Creek - 2008

0

2

4

6

8

10

12

14

+ 10 8 16 19

28 +

33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129

+ 15

813

714

115

115

515

716

917

117

718

0 +

193

187

189

194

200

202

205

207

209

PCB

con

gene

r % o

f tot

al

May 8June 16August 26

Desjardins Canal - 2007

0

2

4

6

8

10

12

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

March 14 (1)March 14 (2)April 27 (1)April 27 (2)May 9 (1)May 9 (2)August 8 (1)August 8 (2)September 11 (1)September 11 (2)September 27 (1)September 27 (2)

Hamilton Harbour Centre Station - 2007

0

2

4

6

8

10

12

14+

10 8 16 1928

+33 37 41 49 54 66 74 81 85 95 99 105

114

119

126

129+

158

137

141

151

155

157

169

171

177

180+

193

187

189

194

200

202

205

207

209

PCB

Con

gene

r % o

f tot

al

April 2 (1)

April 2 (2)

May 31 (1)

May 31 (2)

July 24 (1)

July 24 (2)

Figure 50: PCB congener patterns observed 2008 in Chedoke Creek relative to patterns observed at the Desjardins Canal and Hamilton Harbour Centre Station in 2007.



Centre_Stn_Apr_2_2007(a)Centre_Stn_Apr_2_2007(b)Centre_Stn_May_31_2007(a)Centre_Stn_May_31_2007(b)Centre_Stn_Jul_24_2007(a)

Centre_Stn_Jul_24_2007(b)Desj_Canal_Mar_14_2007(a)

Desj_Canal_Mar_14_2007(b)

Desj_Canal_Apr_27_2007(a)Desj_Canal_Apr_27_2007(b)

Desj_Canal_May_9_2007(a)Desj_Canal_May_9_2007(b)Desj_Canal_Aug_8_2007(a)Desj_Canal_Aug_8_2007(b)Desj_Canal_Sep_11_2007(a)Desj_Canal_Sep_11_2007(b)Desj_Canal_Sep_27_2007(a)Desj_Canal_Sep_27_2007(b)

Chedoke_Ck_May_8_2008Chedoke_Ck_June_16_2008

Chedoke_Ck_Aug_26_2008

A1016

A1242

A1248aA1248g

A1254a

A1254g

A1260

-8 -4 4 8 12 16 20 24

Component 1

-9

-6

-3

3

6

9

12

15

18

Com

pone

nt 2

Centre_Stn_Apr_2_2007(a)

Centre_Stn_Apr_2_2007(b)Centre_Stn_May_31_2007(a)

Centre_Stn_May_31_2007(b)

Centre_Stn_Jul_24_2007(a)

Centre_Stn_Jul_24_2007(b)

Desj_Canal_Mar_14_2007(a)

Desj_Canal_Mar_14_2007(b)

Desj_Canal_Apr_27_2007(a)

Desj_Canal_Apr_27_2007(b)

Desj_Canal_May_9_2007(a)

Desj_Canal_May_9_2007(b)Desj_Canal_Aug_8_2007(a)Desj_Canal_Aug_8_2007(b)

Desj_Canal_Sep_11_2007(a)

Desj_Canal_Sep_11_2007(b)

Desj_Canal_Sep_27_2007(a)Desj_Canal_Sep_27_2007(b)

Chedoke_Ck_May_8_2008

Chedoke_Ck_June_16_2008

Chedoke_Ck_Aug_26_2008

-10 -8 -6 -4 -2 2 4 6

Component 1

-3.6

-3

-2.4

-1.8

-1.2

-0.6

0.6

1.2

Com

pone

nt 2

Figure 51: Principle Component Analysis (PCA) plot for water samples collected during 2008 from Chedoke Creek relative to water samples collected during 2007 at Centre Station and at the Desjardins Canal. Notes: PCA was conducted on PCB signatures standardized to PCB congener % of total so samples could be compared against standard Aroclor signatures. PC1 has eigenvalue of 55.21; % variance is 54.75; PC2 has eigenvalue of 22.61 and % variance of 22.42. PCA run in PAST.exe (Hammer et al. 2001). PCB congener profiles of Centre Station and the Desjardins Canal sampled in 2007 are reported in Labencki (2009). Aroclor profiles from US EPA (2006).



3.6 Sediment Sampling in the Strathearne Avenue Slip Surface sediment sampled from station 366 in the Strathearne Ave Slip during 2008 had a total PCB concentration of 16,273.4 ng/g dw; the total organic carbon (TOC) concentration was 92 mg/g dw. The PCB concentration was approximately an order-of-magnitude greater than the 2003 Windermere Arm surface sediment area-weighted average PCB concentration of 1,270 ng/g (Labencki, 2008) and almost two-orders-of magnitude greater than the sediment probable effect level (PEL) of 277 ng/g (CCME, 2001). The PCB concentration from station 366 was however, less than the site-specific severe effect limit (SEL) of 48,760 ng PCB/g TOC, based on the product of 92 mg/g TOC and the SEL of 530,000 ng PCB/g TOC (MOE, 1993). PCB concentrations much less than the SEL are still of concern however due to biomagnification of PCBs and the resulting BUI Restrictions on Fish and Wildlife Consumption in local fish (Labencki, 2008). Further, the high PCB concentrations in sediment in the Slip have the potential to act as a PCB source area to the rest of the Harbour and may be a significant source of PCBs to the water column. High concentrations of PCBs were measured in the waters of Windermere Arm relative to centre station both in 2007 (Labencki, 2009) and 2008 (3.2 Water Sampling in Hamilton Harbour), suggesting a Harbour PCB source area in the vicinity of Windermere Arm, such as Strathearne Avenue Slip. The PCB congener pattern for the Strathearne Ave Slip surface sediment was also examined to determine similarity to standard Aroclor patterns and PCB congener patterns that have been observed in Windermere Arm. The PCB congener pattern at station 366 showed a similarity to Aroclors 1242, 1254g and 1260 (Figure 52). The high proportion of A1242 in the 2008 Strathearne Ave Slip sediment sample is consistent with results of sediment sampling conducted at nearby station 7057 in 2000, where A1242 constituted approximately 46% of a total PCB concentration of 5,200 ng/g (Milani and Grapentine, 2006a). While it remains possible that Aroclor 1242 is present in sediment samples from the Strathearne Ave Slip, the congener pattern observed in the sediments relative to Aroclor 1242 is not an exact match. The presence of the high proportion of less-chlorinated congeners in the sample may alternatively be the result of some kind of alteration process such as dechlorination, as dechlorinated Aroclor 1254 has a congener pattern similar to Aroclor 1242 (Johnson et al., 2006).



a) Strathearne Ave Slip surface sediments, 2008

0

2

4

6

8

10

12

14

PC

B01

8P

CB

022

PC

B03

3P

CB

044

PC

B05

2P

CB

070

PC

B07

7P

CB

087

PC

B09

9P

CB

104

PC

B11

0P

CB

118

PC

B12

3P

CB

128

PC

B14

9P

CB

153

PC

B15

6P

CB

158

PC

B16

8P

CB

170

PC

B17

7P

CB

180

PC

B18

7P

CB

189

PC

B19

4P

CB

201

PC

B20

5P

CB

208

PCB

Con

gene

r % o

f Tot

al P

CB

Station 366

40% A1242, 40% A1254g, 20% A1260

b) Windermere Arm surface sediments, 2003 (0-10 cm depth interval)

0

2

4

6

8

10

12

14

PC

B01

8P

CB

022

PC

B03

3P

CB

044

PC

B05

2P

CB

070

PC

B07

7P

CB

087

PC

B09

9P

CB

104

PC

B11

0P

CB

118

PC

B12

3P

CB

128

PC

B14

9P

CB

153

PC

B15

6P

CB

158

PC

B16

8P

CB

170

PC

B17

7P

CB

180

PC

B18

7P

CB

189

PC

B19

4P

CB

201

PC

B20

5P

CB

208

PCB

Con

gene

r % o

f Tot

al P

CB

WA03WA06WA07WA08WA11WA13WA16WA21WA22WA2440% A1254g, 60% A1260

Figure 52: PCB congener patterns in a) Strathearne Ave Slip surface sediment; and b) Windermere Arm surface sediment. Notes: Windermere Arm surface sediment was sampled December 2003 (Labencki, 2008). Aroclor profiles from US EPA (2006). The PCB congener pattern of sediment sampled from station 366 differs greatly from that observed in Windermere Arm surface sediment (Figure 52). The sediments in Windermere Arm show a strong similarity to Aroclors 1254g and 1260, and while the sediments in Strathearne Ave slip also show evidence of these Aroclor mixtures in sediment, the Strathearne sediments also have a high proportion of less-chlorinated congeners relative to the Windermere Arm sediments. As noted above, it is unknown whether the presence of these tri- and tetra-chlorinated biphenyls are due to an additional source (i.e. Aroclor 1242) or due to dechlorination of Aroclor 1254g and/or possibly Aroclor 1260, the latter of which is more resistant to breakdown. The



conditions (e.g. dissolved oxygen, redox, etc.) in the Strathearne Ave Slip may be quite different from those in Windermere Arm, potentially explaining differences in relative dechlorination rates between sites. Reasons for the different PCB congener pattern in the Strathearne Ave slip, be it a different/additional PCB source or dechlorination, should be further investigated to determine the role of the Strathearne Ave slip in the PCB dynamics of Hamilton Harbour, especially considering the very high total PCB concentrations measured in the Slip in all media sampled during 2008 . Polycyclic Aromatic Hydrocarbon (PAH) Concentration

Due to observations of persistent oil sheens in the Slip (3.1 General Field Observations), observation of product in the sediment sample and a strong petroleum odour, the station 366 surface sediment sample was also analyzed for PAHs. The station 366 surface sediment sample had a total PAH concentration (Σ18PAH) of 5,731.1 ug/g dw or approximately 0.5% PAH. This PAH concentration is on par with PAH concentrations measured in the most contaminated area surrounding Randle Reef (Milani and Grapentine, 2006b). The total PAH concentration was approximately six times greater than the site-specific SEL of 920 ug PAH/g TOC, based on the product of 92 mg/g TOC and the SEL of 10,000 ug PAH/g TOC (MOE, 1993). The PAH compound pattern for the Strathearne Ave Slip surface sediment was also examined (Figure 53). The three most prevalent PAH compounds in the sediment sample were phenanthrene (30% of total), fluoranthene (14% of total) and pyrene (10% of total). Results of water sampling conducted during 2007 demonstrated that pyrene and fluoranthene were the most prevalent PAH compounds in the water column of the Harbour (Labencki, 2009). The detection of high concentrations of phenanthrene in sediment is of interest for this reason, and also because it is of lower molecular weight relative to fluoranthene and pyrene, and should have a higher tendency to desorb from sediments to the water column, and volatilize. Similarly, the relatively high presence of naphthalene in the sediment sample suggests that the source of these PAHs in the Strathearne Ave slip may be recent, or that another process is preventing the loss of lower molecular weight PAH compounds from the sediment to the water column.



0200400600800

10001200140016001800

Nap

htha

lene

Acen

apht

hyle

ne

Acen

apht

hene

Fluo

rene

Phen

anth

rene

Ant

hrac

ene

Fluo

rant

hene

Pyr

ene

Benz

o(a)

anth

race

ne

Chr

ysen

e

Benz

o(b)

fluor

anth

ene

Benz

o(k)

fluor

anth

ene

Ben

zo(e

)pyr

ene

Ben

zo(a

)pyr

ene

Per

ylen

e

Inde

no(1

,2,3

-c,d

)pyr

ene

Dib

enzo

(a,h

)ant

hrac

ene

Benz

o(g,

h,i)p

eryl

ene

PAH

(ug/

g dw

)

Figure 53: PAH compound profile for surface sediment from Station 366 in Strathearne Ave Slip. Although biological toxicity testing has not been performed on sediment from Station 366, due to exceedence of the PAH SEL, the sediment is likely acutely toxic to benthos. During visual inspection of the sediment sample, globules of product were noted in the sediment and on the water that collected in the sampling pan. The sediment had a very strong petroleum odour and a runny consistency (Figure 11), and was contaminated with a non-aqueous phase liquid (NAPL), possibly coal tar. Sediments from the bottom of the Strathearne Avenue Slip may be the source of the oil sheens consistently noted on the water surface in the Slip during the 2008 field season (Figure 13). In addition to the high PAH concentrations in the sediment, the physical nature of the sediment at station 366 may also contribute towards acute toxicity to benthos, as was suspected in toxicity observed for PAH-contaminated sediments collected from Randle Reef in 2005 and 2006 (US EPA, 2007, p.101).

For reasons of both potential PCB bioaccumulation and acute toxicity to benthos, it is recommended that further sediment sampling be conducted along the length of the Strathearne Ave Slip to determine the extent and nature of contamination in the Slip, as well as its potential for acting as a PCB source area to the rest of the Harbour.



4. Conclusions Analysis of data collected during the 2008 field season in Hamilton Harbour resulted in several important conclusions relevant to the Hamilton Harbour RAP. Several media were sampled to meet the objectives of the field season, including water sampling at 9 stations in the Harbour (depth-integrated and bottom grab samples), semi-permeable membrane device (SPMD) deployment at 10 stations in the Harbour (including Cootes Paradise), sludge sampling at the three Waste Water Treatment Plants (WWTPs), event-based water sampling in Chedoke Creek and sediment sampling in the Strathearne Avenue Slip. While the conclusions formed on the 2008 field season would not likely change if sampling were conducted during a different year, important to note is that the summer of 2008 was an unusually wet summer (Environment Canada, 2008b). The primary objective of the field season was to determine if there are any active, locally-controllable PCB sources to Hamilton Harbour following the finding of anomalously high PCB concentrations in the Harbour during the 2007 field season (Labencki, 2009). A second objective in concert with the first was to evaluate whether internal PCB cycling/resuspension from historically-contaminated sediment plays a large role in the high PCB concentrations in Hamilton Harbour water and sediment. Data collected at each station sampled either suggested the presence of a potential PCB source requiring further follow-up, or that the area can be discounted from further PCB trackdown work: 1. Windermere Arm remains the primary PCB source area to Hamilton Harbour.

Spatial variability data analyses suggest that any follow-up on further understanding PCB fate and transport mechanisms in the Harbour should be focused on Windermere Arm, where differences in spatial trends both for total PCB concentrations and PCB congener signatures are more pronounced relative to the main basin of the Harbour. There was more spatial differentiation for surface-integrated samples relative to bottom grab samples, suggesting much of the spatial variability is due to processes occurring in the upper water column. Overall, data suggest episodic inputs of PCBs to Windermere Arm, which is likely acting as a source area to the main basin of the Harbour, where total PCB concentrations varied little between surveys, and total PCB concentrations and PCB congener signatures varied little between stations all suggesting that PCB concentrations in the main basin of the Harbour appear relatively well mixed.



2. Resuspension of PCB-contaminated sediment is likely occurring periodically throughout Windermere Arm to maintain high background levels of PCB in the water column throughout the Harbour.

Resuspension of in situ surface sediment does not appear to be a consistent source of PCBs to the water column on a Harbour-wide basis, as differences in temporal dynamics between PCB and TSS concentrations in the Harbour were observed. As such, TSS concentrations are not a good proxy for tracking PCB concentration dynamics and trends in the Harbour, further supported by the finding of relatively high concentrations of less-chlorinated congeners in the Harbour. However, there is circumstantial evidence that resuspension may contribute towards elevated PCB concentrations sporadically in localized areas of the Harbour (e.g. areas within Windermere Arm), which after mixing, may eventually form the background conditions in the rest of the Harbour. This hypothesis is consistent with similar findings by Slater et al. (2008) for PAHs, as a harbour-wide increase in PAH depositions appeared to be originating from a source to Windermere Arm. Localized resuspension is likely driven by varying shear stresses throughout the Harbour due to both natural (i.e. wind, wave action; Brassard and Morris, 1997) and anthropogenic sources (i.e. ship traffic; Irvine et al., 1997), in combination with the susceptibility of the local sediment to erosion. Erosion can differ greatly between different areas of the Harbour due to sediment characteristics such as density and (Krishnappan and Droppo, 2006) and grain size (Brassard and Morris, 1997). In particular, resuspension of contaminated sediment may be a PCB source to the ArcelorMittal Dofasco Boat Slip consistent with historical studies in the Slip (Irvine et al., 1997; Jaagumagi et al., 2003). Resuspension in this study was suggested by:

• consistently high total PCB concentrations in the Slip despite variation in antecedent weather conditions;

• empirical data analysis of turbidity profile data in the Slip; • measured PCB concentration in surface sediment high enough to explain

measured whole water PCB concentrations; and • PCB congener profile in both water and SPMDs are consistently enriched in

more-chlorinated congeners, a signature consistent with a sediment source due to the affinity of more-chlorinated congeners with particles.

3. Episodic inputs of significant, external PCB source(s) may be entering the

Harbour via the Windermere Basin, the ArcelorMittal Dofasco Boat Slip, and particularly the Strathearne Avenue Slip.

Results of water sampling in 2008 were inconclusive as to whether an external source or resuspension is the primary driver of elevated PCB concentrations in the Harbour, and in fact, both may be contributing depending on circumstances. While



ongoing resuspension of PCB-contaminated sediment in Windermere Arm may form background conditions in the Harbour, periodic PCB inputs from external sources may also be contributing to isolated PCB concentration anomalies in areas within Windermere Arm. Anomalously high mean PCB concentrations were measured in both water and SPMDs during the 2008 field season from:

• The Windermere Basin/Arm bridge (surface-integrated samples: 37 ng/L; bottom grab samples: 38 ng/L; SPMDs: 2,127 ng/mL triolein);

• The Strathearne Avenue Slip (surface-integrated samples: 108 ng/L; bottom grab samples: 90 ng/L; SPMDs: 13,137 ng/mL triolein), and;

• The ArcelorMittal Dofasco Boat Slip (surface-integrated samples: 113 ng/L; bottom grab samples: 80 ng/L; SPMDs: 4,270 ng/mL triolein)

PCB concentrations in water were particularly high at Windermere Arm stations 268, 352 and 366 during the August 19 survey which followed a large precipitation event to the Harbour on August 18, which in addition to a lack of correlation with TSS concentrations on this date suggests potential PCB inputs from the sewer/watersheds. The presence of an active, ongoing PCB source is particularly suspected in the Strathearne Avenue Slip. In this Slip, mean total PCB concentrations in SPMDs (~13,000 ng/mL triolein) were over two orders-of-magnitude greater than ambient lake concentrations (~40 ng/mL triolein), over one order-of-magnitude greater than ambient concentrations in the main basin of Hamilton Harbour (~400 ng/mL triolein) and approximately three fold greater than the maximum concentrations found in the MOE’s PCB Trackdown Project (~4,900 ng/mL triolein). The PCB congener signature at both the Windermere Arm/Basin Bridge and in the Strathearne Avenue Slip was enriched in less-chlorinated congeners and was similar to the signature observed in final effluent sampled from the Woodward Avenue WWTP during 2007. This similarity in signature as well as the patterns in temporal variability in total PCB concentrations suggest that the Parkdale and Strathearne Ave combined sewer overflows (CSOs) may be potential ongoing sources of PCBs to Windermere Arm.

4. Persistent oil sheens and anomalously high PCB and PAH concentrations in

sediment were observed in the Strathearne Avenue Slip.

Resuspension of bottom sediments at station 366 did not appear to be the primary driver of elevated PCB concentrations at this station, perhaps due to the tarry nature of the bottom sediment which may be cohesive and resistant to erosional forces. However, PCB-contaminated sediment may still be a contributor towards the elevated PCB concentrations in the water column at this site as oil sheens (potentially contaminated with PCBs) were regularly observed in the Strathearne Avenue Slip, which appeared to be sourced from the sediments in the Slip. Thus,



the PCB-contaminated sediment at station 366 cannot be removed as a potential PCB source to the Slip and the Harbour in general.

5. Data did not support the presence of an ongoing, local source of PCB to the

main basin of the Harbour and thus follow-up PCB trackdown investigations in the main basin of the Harbour are not warranted.

Results of both water sampling and SPMD deployment supported this conclusion as there were no spatial gradients in total PCB concentration for stations located within the main basin of the Harbour, and also there were no differences in PCB congener profiles between stations. Further, the relatively low PCB concentrations in water and SPMDs deployed at station 367 suggest that the north shore is not a PCB source area which resolves any previous concerns regarding a potential PCB source near LaSalle Park Pier as documented in Harlow and Hodson (1988).

6. Data did not support the presence of an ongoing, local source of PCBs to

Cootes Paradise, including Chedoke Creek, and thus follow-up PCB trackdown investigations in Cootes Paradise and Chedoke Creek are not warranted.

The relatively high PCB concentration measured in the Desjardins Canal water during 2007 was likely due to backflow of water from Hamilton Harbour, and not due to a local PCB anomaly in Cootes Paradise. Results of the SPMD deployment in Cootes Paradise, sludge sampling at the Dundas WWTP and event-based water sampling in Chedoke Creek are several lines-of-evidence which support this conclusion. The SPMDs deployed in Cootes Paradise had PCB concentrations high in comparison to ambient lake conditions; however, concentrations during both deployments were still the lowest of all stations where SPMDs were deployed in Hamilton Harbour. Next, PCB concentrations in sludge from the Dundas WWTP were on par with concentrations from the Skyway WWTP and low relative to the Woodward Ave WWTP, suggesting PCB contributions to the Dundas (i.e. Cootes Paradise) sewershed are low relative to the Hamilton sewershed, where historical PCB use is known to have occurred. Finally, results of event-based water sampling in Chedoke Creek demonstrated that PCB concentrations in the creek are consistent with urban background levels and not suggestive of a local anomaly requiring follow-up action.



A third objective of the 2008 field season was to evaluate how fate and transport of PCBs in Hamilton Harbour play into the PCB concentrations observed in the local foodweb. While a definitive conclusion regarding this objective is not possible at this time, there may be biological implications of the unique PCB congener profile observed in water and SPMD samples from the Strathearne Avenue Slip and at the Windermere Basin Bridge: 7. The enrichment of less-chlorinated PCB congeners in water seemingly

sourced from the Strathearne Avenue Slip and the Windermere Basin may be playing a role for a relatively high pelagic exposure of PCBs in the water column of Hamilton Harbour, which may be factoring into relatively high bioaccumulation of PCBs to the local food web.

A fourth objective of the 2008 field season was to determine if there are any remedial and/or management actions possible to address the BUI Restrictions on Fish and Wildlife Consumption. Several follow-up actions were recommended in response to the results of the 2008 field season, as discussed below in Section 5. Recommendations. The last objective of the 2008 field season was to evaluate whether PCB exposure to young-of-the-year (YOY) fish has increased in recent years. Sampling of YOY fish was planned for 2008 due to elevated PCB concentrations observed during 2006 and lack of data for the 2007 field season; however, sampling was again forfeited in 2008 due to the inability to obtain YOY fish samples at locations surveyed.



5. Recommendations

As follow-up to the sampling conducted in Hamilton Harbour during 2008, several recommendations have been formed to advance actions towards delisting the relevant BUI under the Hamilton Harbour RAP. These recommendations include: 1. Water from the Parkdale, Strathearne Ave and Kenilworth CSOs should be

sampled during overflow events to determine if these CSOs are conveying an ongoing, active source of PCBs to the Windermere Basin, Strathearne Avenue Slip and ArcelorMittal Dofasco Boat Slip, respectively. The historical presence of high PCB concentrations in Windermere Basin (Harlow and Hodson, 1988) and in water from the Strathearne Avenue CSO (MOE, 1985) in addition to anomalously high PCB concentrations measured in water and SPMDs from stations 268, 366 and 369 during 2008 suggest that the Parkdale, Strathearne and Kenilworth CSOs should be investigated to evaluate whether they are acting as a conduit for an active, locally-controllable source of PCBs to the Harbour. Water collected from inside the combined sewer system, upstream from all three respective CSO discharge points should be analyzed for TSS and PCB congeners. This sampling will also assist in interpretation of the anomalous PCB congener signature observed in water and SPMDs at stations 268 and 366 during 2008, which appeared similar to the signature observed in effluent from the Woodward Ave WWTP sampled in 2007. In addition, event-based sampling in the Harbour adjacent to the CSO discharge locations may supplement CSO investigations.

2. Sediment cores should be collected along a north-south transect in the

Strathearne Avenue Slip to determine the extent and nature of sediment contamination in the Slip.

Sediment cores from the Strathearne Ave Slip should be analyzed for PCBs to help evaluate whether sediment from the Slip is a significant source of elevated PCB concentrations in the Harbour. The inclusion of PCB congeners in analysis will assist in determining the reason(s) for differences in PCB congener patterns between those observed at station 366 and the rest of Windermere Arm, be it perhaps dechlorination in the sediments or an external PCB source to the Slip. Sediment analysis should also include PAHs and oil/grease proxies to help evaluate whether the sediments are the source of persistent oil sheens in the Strathearne Avenue Slip, and also the potential for benthic toxicity in the Slip. In addition, water samples should also be collected at sediment coring stations to supplement sediment investigations and determine the nature of any PCB water concentration



gradients in the Slip. Any follow-up work in the Strathearne Avenue Slip should note the potential for the presence of contaminants at hazardous waste levels at this station, and precautions should be taken accordingly.

3. An ADCP current meter should be installed in the Strathearne Avenue Slip to

estimate PCB loads from the Slip and help evaluate if the Strathearne Ave Slip is overall a source or sink of PCB contamination in context of Windermere Arm.

Current meter data will assist in determining the potential impact of contamination from the Strathearne Avenue Slip to areas outside the Slip and the extent to which this Slip is a PCB source to the Harbour in general. ADCP current meter data will also assist in the calculation of the PCB load attributable to the Slip relative to other PCB sources to Windermere Arm.

4. YOY fish sampling should be re-attempted in 2009 at the locations sampled in

2006 (Grindstone Creek, CCIW) to determine if elevated PCB concentrations observed in 2006 were part of the natural variability or if biological exposure to PCBs has increased in recent years.

5. Any follow-up on further understanding PCB fate and transport mechanisms

in the Harbour should focus on Windermere Arm, where differences in spatial trends both for total PCB concentrations and PCB congener signatures are more pronounced relative to the main basin of the Harbour.

There was more spatial differentiation for surface-integrated samples relative to bottom grab samples, suggesting much of the spatial variability is due to processes occurring in the upper water column in Windermere Arm. In addition, PCB dynamics in the Strathearne Ave and the ArcelorMittal Dofasco Slips in particular remain complex and because these Slips are potentially significant in terms of being overall Harbour PCB sources, further analysis of PCB dynamics at these stations in particular is recommended to be included in any further work on PCBs in Hamilton Harbour.



6. Work should continue on implementing the sediment management strategy for contaminated sediment in the ArcelorMittal Dofasco Boat Slip.

Resuspension of contaminated bottom sediments in the ArcelorMittal Dofasco Boat Slip was suggested by the 2008 dataset, consistent with historical studies (e.g. Irvine et al., 1997; Jaagumagi et al., 2003) which have previously noted this issue. Follow-up remedial actions by ArcelorMittal Dofasco for addressing contaminated sediment in the boatslip are currently underway, and it is recommended that ArcelorMittal Dofasco continue towards completion of these remedial actions, as has been documented in the BAIT Workplan. The completion of the sediment management strategy for the Slip may have cascading benefits for other parts of the Harbour as immobilization of bed material from the ArcelorMittal Dofasco Boat Slip may reduce redistribution of contaminated sediment to other cleaner parts in the Harbour (Irvine et al., 1997).

7. Examine if mitigation measures are necessary for reducing sediment

resuspension due to the passage of vessels in areas of high sediment contamination, e.g. Windermere Arm. To assist with this determination, sediment traps should be deployed in key locations. Windermere Arm is not only a Harbour hotspot for elevated PCB concentrations, but is also an area with an active shipping channel and several Piers. In the investigation of practices which would minimize contaminated sediment resuspension, both the susceptibility of sediments to erosion, such as density (Krishnappan and Droppo, 2006) needs to be considered, as well as the presence of sheer stresses, such as that caused by ship traffic. As previous studies have found that Windermere Arm sediment is erodable (Krishnappan and Droppo, 2006), and due to a finding of resuspension and redistribution of sediment-derived contaminants from Windermere Arm, immobilization of Windermere Arm sediment has previously been recommended (Slater et al., 2008). Reducing if not preventing resuspension of contaminated sediment in an active shipping area of the Harbour is challenging, but some success has been realized in other similar areas through various control measures. For example, for contaminated areas along the Seattle waterfront, “anthropogenic influences can be at least as important in determining contaminant transport in sediments as natural processes” (Michelsen et al., 1998, p.15); that is, prop wash from vessels was found to play a major role in resuspension events that were capable of recontaminating adjacent areas (Michelsen et al., 1998). In response to the Seattle study,

to reduce liability and prevent the spread of contamination in sediments, various



measures [were] under consideration by the agencies, Port, and ferry system, including vessel designs that minimize turbulence at the bed, operational constraints (such as speed limits), terminal and pier design to place vessels in deeper water, use of concrete or steel pilings that require less maintenance, banning of high-disturbance construction practices (such as jetting) in contaminated areas, and better scheduling and coordination between cleanup and construction projects (Michelsen et al., 1998, p.15).

Although focused on the ArcelorMittal Dofasco Boat Slip but may be applicable elsewhere in the Windermere Arm, Irvine et al. (1997) recommended that an examination take place of potential modifications to shipping operations that may reduce sediment resuspension. These potential modifications include “deeper dredging near sensitive areas, “light-loading” ships, changes in the operation of bow thrusters and propellers, or development of alternative shipping channels” (Irvine et al., 1997, p.434). While controls on vessel traffic will likely help reduce resuspension of contaminated sediment, particularly in problematic areas like Windermere Arm, it remains that even in the absence of vessel traffic, resuspension will nonetheless continue to occur in the Harbour to some extent due to natural processes such as wind and wave driven forces (Brassard and Morris, 1997); albeit perhaps at slower rates. As such, this places higher emphasis on addressing local contaminant hotspots, before sediments are redistributed to the water column and become part of future Harbour background water and sediment concentrations. Investigation of contaminant concentration data collected through the deployment of sediment traps in the Harbour can assist in any evaluations of resuspension of contaminated bottom sediment.



6. References ASI Group Ltd. 2006. Environmental Assessment of Wellington Street, Emerald Street,

Strathearne Avenue, and Wentworth Street Slips. Final Report. September 20, 2006.

Booij, K., Hofmans, H.E., Fischer, C.V. and E.M. VanWeerlee. 2003. Temperature-

Dependent Uptake Rates of Nonpolar Organic Compounds by Semipermeable Membrane Devices and Low-Density Polyethylene Membranes. Environ. Sci. Technol. 37: 361-366.

Bowman, J.E., and T. Theysmeyer. 2008. Supplementary Marsh Sediment

Characterization; Carroll’s Bay and West Pond Areas. RBG Report No. 2008-02. Royal Botanical Gardens. Hamilton, Ontario.

Bowman, J. 2007. 2006 Cootes Paradise Sediment Quality Assessment. Royal

Botanical Gardens. March 2007. Boyd, D. 2001. A summary of Contaminants in suspended sediment at sources to

Hamilton Harbour, Technical Memorandum prepared for the Hamilton Harbour Remedial Action Plan, Environmental Monitoring and Reporting Branch, Updated July 2001.

Brassard, P. and W. Morris. 1997. Resuspension and Redistribution of Sediments in

Hamilton Harbour. J. Great Lakes Res. 23 (1): 74-85. Canadian Council of Ministers of the Environment (CCME). 2001. Canadian sediment

quality guidelines for the protection of aquatic life: Polychlorinated biphenyls (PCBs). Updated. In: Canadian environmental quality guidelines, 1999, Canadian Council of Ministers of the Environment, Winnipeg.

City of Hamilton Public Works Department. Waste Management Division. 2008.

Annual Monitoring Report – 2007. Rennie and Brampton Closed Landfill Sites. Final Report. March 2008.

De Solla, S.R., Fernie, K.J., Letcher, R.J., Chu, S.G., Drouillard, K.G. and S. Shahmiri.

2007. Snapping Turtles (Chelydra serpentina) as Bioindicators in Canadian Areas of Concern in the Great Lakes Basin. 1. Polybrominated Diphenyl Ethers, Polychlorinated Biphenyls, and Organochlorine Pesticides in Eggs. Environmental Science and Technology. 41. pp. 7252 -7259.



Environment Canada. 2008a. Daily Observation Data | Canada’s National Climate Archive. National Climate Data and Information Archive. [online]. Data modified 2008-10-09. Available: http://www.climate.weatheroffice.ec.gc.ca/climateData/dailydata_e.html?timeframe=2&Prov=XX&StationID=4932&Year=2008&Month=9&Day=1 [August 21, 2009].

Environment Canada. 2008b. Canada’s Top 10 Weather Stories for 2008. 1. The

East’s Big Summer Soak. [online]. Available: http://www.ec.gc.ca/doc/smc-msc/2008/s1_eng.html. [October 28, 2010].

Erickson, M.D. 1997. Analytical Chemistry of PCBs. Second Edition. Lewis

Publishers. Gandhi, N. and M. Diamond. 2005 (unpublished). Preliminary Fate-Transport Modeling

Results for Total PCB in Hamilton Harbour. February 4, 2005. Gondim, F. and C. Murdoch. 2009. Fifty years of remediation projects at West

Hamilton Closed Landfill. Environmental Science & Engineering Magazine. Summer 2009. p.50-51.

Gondim, F. and C. Murdoch. 2008. Challenges and opportunities to remediate closed

landfill sites. Environmental Science & Engineering Magazine. January 2008. p. 56-58.

Hamilton Harbour Remedial Action Plan (HH RAP). 2006. BAIT 2006-2011 Workplan.

November 24, 2006. Hamilton Harbour Remedial Action Plan (HH RAP). 2003. Remedial Action Plan for

Hamilton Harbour: Stage 2 Update 2002. ISBN 0-9733779-0-9. June 2003. Hamilton Harbour Remedial Action Plan (HH RAP). 1998. 1998 Status Report. ISBN

0-662-27238-2. September, 1998. Hamilton Harbour Remedial Action Plan (HH RAP). 1992. Environmental Conditions

and Problem Definition. Second Edition of the Stage 1 Report. ISBN 0-7778-0174-4. October 1992.

Hamilton Port Authority (HPA). 2008. Hamilton Port Authority – Vessel Tracking.

[online]. Available: www.hamiltonport.ca/commercial/vesseltracking.aspx [Accessed May - September, 2008].

Hammer, Ø., Harper, D.A.T., and P. D. Ryan, 2001. PAST: Paleontological Statistics



Software Package for Education and Data Analysis. Palaeontologia Electronica 4(1): 9pp.

Harlow, H.E. and P.V. Hodson. 1988. Chemical Contamination of Hamilton Harbour: A

Review. Canadian Technical Report of Fisheries and Aquatic Sciences No. 1603. pp. 91.

Holmes, J.A. 1986. The Impact of Dredging and Spoils Disposal on Hamilton Harbour

Fisheries: Implications for Rehabilitation. Canadian Technical Report of Fisheries and Aquatic Sciences 1498.

Irvine, K.N., Droppo, I.G., Murphy, T.P., and A. Lawson. 1997. Sediment

Resuspension and Dissolved Oxygen Levels Associated with Ship Traffic: Implications for Habitat Remediation. Water Qual. Res. J. Canada. Vol. 32 (No. 2): pp.421-437.

Jaagumagi, R., Bedard, D., Lomas-Jylha, T., Charlton, M. and Milne, J. 2003.

unpublished. Dofasco Boatslip Assessment of Sediment Contamination. Summary of Investigations Prior to 1997 and 1997, 1998 and 1999 Sediment and Biological Investigations. January 2003.

Johnson, G.W., Quensen, J.F., Chiarenzelli, J.R. and M.C. Hamilton. 2006.

Polychlorinated Biphenyls. In: Environmental Forensics: Contaminant Specific Guide. By: Robert D. Morrison and Brian L. Murphy. Elsevier Science and Technology.

Kleinfeldt Consultants Limited. 1990. Canadian Great Lakes Basin Intake-Outfall Atlas.

Volume 7 Lake Ontario. Prepared for the Ontario Ministry of the Environment. August 1990. ISBN 0-7729-5511-5. Published by the Ontario Ministry of the Environment. ISBN 0-7729-5511-5.

Krishnappan, B.G. and I. Droppo. 2006. Use of an in situ erosion flume for measuring

stability of sediment deposits in Hamilton Harbour, Canada. Water, Air, and Soil Pollution: Focus. 6: pp. 557–567.

Labencki, T. 2009. 2007 Field Season in the Hamilton Harbour Area of Concern. PCB

and PAH water monitoring undertaken to support mass balance work by the Hamilton Harbour Remedial Action Plan (RAP) on PAH contamination at Randle Reef and PCB contamination in Windermere Arm. Hamilton Harbour RAP Toxic Substances and Sediment Technical Team. ISBN: 978-0-9810874-3-6 (Online Version). December 2009.

Labencki, T. 2008. An Assessment of Polychlorinated Biphenyls (PCBs) in the

Hamilton Harbour Area of Concern (AOC) in Support of the Beneficial Use



Impairment (BUI): Restrictions on Fish and Wildlife Consumption. Hamilton Harbour RAP Toxic Substances and Sediment Technical Team. ISBN: 978-0-9810874-1-2 (Online Version). August 2008.

Michelsen, T.C., Boatman, C.D., Norton, D., Ebbesmeyer, C.C. and M.D. Francisco.

1998. Transport of Contaminants along the Seattle Waterfront: Effects of vessel traffic and waterfront construction activities. Wat. Sci. Tech. Vol. 37, No. 6-7, pp.9-15.

Milani, D. and L.C. Grapentine. 2006a. Application of BEAST sediment quality

guidelines to Hamilton Harbour, An Area of Concern. NWRI Contribution No. 06-407.

Milani, D. and L.C. Grapentine. 2006b. Identification of Toxic Sites in Hamilton

Harbour. Environment Canada. NWRI Contribution No. 06-408. Mudroch, A., Onuska, F.I. and L. Kalas. 1989. Distribution of Polychlorinated Biphenyls

in Water, Sediment and Biota of Two Harbours. Chemosphere. 18: 2141-2154. New York Academy of Sciences (NYAS). 2005. Pollution Prevention and Management

Strategies for Polychlorinated Biphenyls in the New York/New Jersey Harbor. Authored by: Marta Panero, Susan Boehme and Gabriela Muñoz.

Ontario Ministry of the Environment (MOE). 2007. [online]. Environmental Protection

Act. R.R.O. 1990, REGULATION 362 WASTE MANAGEMENT — PCB’S. Last amendment: O.Reg. 33/07. Available: http://www.e-laws.gov.on.ca/html/regs/english/elaws_regs_900362_e.htm [Accessed: August 10, 2010].

Ontario Ministry of Environment and Energy (MOEE). 1994. Policies Guidelines

Provincial Water Quality Objectives of the Ministry of Environment and Energy. Queen’s Printer for Ontario. July 1994.

Ontario Ministry of the Environment (MOE). 1993. Guidelines for the Protection and

Management of Aquatic Sediment Quality in Ontario. Queen’s Printer for Ontario. August 1993.

Ontario Ministry of the Environment (MOE). 1986. Hamilton Harbour Trace

Contaminants – 1982-83 Loadings to, and concentrations in the Harbour. July 1986.

Ontario Ministry of the Environment (MOE). 1985. Hamilton Harbour Technical

Summary and General Management Options. ISBN 0-7729-0706-4. August, 1985.



Ontario Ministry of the Environment (MOE). 1974. Hamilton Harbour Study. May 1974. Rantalainen, A.L., Cretney, W.J. and M.G. Ikonomou. 2000. Uptake rates of

semipermeable membrane devices (SPMDs) for PCDDs, PCDFs and PCBs in water and sediment. Chemosphere. 40: 147-158.

Rao, Y.R., Marvin, C.H., and J. Zhao. 2009. Application of a numerical model for

circulation, temperature and pollutant distribution in Hamilton Harbour. Journal of Great Lakes Research. 35: 61-73.

Slater, G.F., Cowie, B.R., Harper, N. and I.G. Droppo. 2008. Variation in PAH inputs

and microbial community in surface sediments of Hamilton Harbour: Implications to remediation and monitoring. Environmental Pollution. 153: 60-70.

United States Environmental Protection Agency (US EPA). 2006. PCB ID - Downloads

and Data Dictionary. [Online]. Available: http://www.epa.gov/toxteam/pcbid/down.htm. [July 27, 2007].

United States Environmental Protection Agency (US EPA). 2007. Sediment Toxicity

Identification Evaluation (TIE) Phases I, II, and III Guidance Document EPA/600/R-07/080. Office of Research and Development. Washington, DC



Appendix I: May – September 2008 weather conditions in Hamilton Data from Hamilton A Station (43° 10.301' N, 79° 56.051' W), Environment Canada (2008a).

Daily Data Report for May 2008

D a y

Max Temp

°C

Min Temp

°C

Mean Temp

°C

Heat Deg Days

°C

Cool Deg Days

°C

Total Rainmm

Total Snow

cm

Total Precip

mm

Snow on Grnd

cm

Dir of Max Gust

10's Deg

Spd of Max Gust km/h

01 10.3 0.2 5.3 12.7 0.0 T 0.0 T 0 5 43 02 7.0 5.1 6.1 11.9 0.0 11.8 0.0 11.8 0 4 46 03 19.2 5.8 12.5 5.5 0.0 16.8 0.0 16.8 0 19 52 04 13.3 3.9 8.6 9.4 0.0 0.4 0.0 0.4 0 23 59 05 20.0 2.3 11.2 6.8 0.0 0.0 0.0 0.0 0 23 43 06 17.7 5.6 11.7 6.3 0.0 0.0 0.0 0.0 0 <31 07 21.2 6.8 14.0 4.0 0.0 9.2 0.0 9.2 0 22 48 08 14.6 5.8 10.2 7.8 0.0 0.0 0.0 0.0 0 30 46 09 14.0 5.8 9.9 8.1 0.0 0.0 0.0 0.0 0 5 54 10 18.9 7.5 13.2 4.8 0.0 0.0 0.0 0.0 0 <31 11 12.2 7.3 9.8 8.2 0.0 3.4 0.0 3.4 0 4 33 12 15.1 8.2 11.7 6.3 0.0 2.8 0.0 2.8 0 <31 13 21.2 6.1 13.7 4.3 0.0 0.0 0.0 0.0 0 <31 14 17.2 6.8 12.0 6.0 0.0 3.2 0.0 3.2 0 20 63 15 17.5 2.9 10.2 7.8 0.0 0.0 0.0 0.0 0 <31 16 17.7 8.3 13.0 5.0 0.0 0.0 0.0 0.0 0 19 33 17 18.5 5.6 12.1 5.9 0.0 1.4 0.0 1.4 0 25 61 18 10.8 3.7 7.3 10.7 0.0 4.4 0.0 4.4 0 29 59 19 10.2 3.1 6.7 11.3 0.0 0.0 0.0 0.0 0 28 59 20 16.9 2.5 9.7 8.3 0.0 T 0.0 T 0 29 37 21 9.7 3.0 6.4 11.6 0.0 0.4 0.0 0.4 0 28 50 22 14.1 4.5 9.3 8.7 0.0 2.0 0.0 2.0 0 29 44 23 18.1 4.0 11.1 6.9 0.0 0.0 0.0 0.0 0 <31 24 19.5 4.8 12.2 5.8 0.0 0.0 0.0 0.0 0 <31 25 21.9 5.8 13.9 4.1 0.0 0.0 0.0 0.0 0 21 44 26 26.9 9.6 18.3 0.0 0.3 1.8 0.0 1.8 0 22 43 27 18.1 2.9 10.5 7.5 0.0 0.0 0.0 0.0 0 <31 28 17.5 2.5 10.0 8.0 0.0 0.0 0.0 0.0 0 25 37 29 23.3 3.6 13.5 4.5 0.0 0.0 0.0 0.0 0 28 37 30 20.2 6.2 13.2 4.8 0.0 8.6 0.0 8.6 0 21 48 31 24.6 11.1 17.9 0.1 0.0 2.2 0.0 2.2 0 33 44 Sum 213.1 0.3 68.4 0.0 68.4 Avg 17.0 5.2 11.1 Xtrm 26.9 0.2 20 63



Daily Data Report for June 2008

D a y

Max Temp

°C

Min Temp

°C

Mean Temp

°C

Heat Deg Days

°C

Cool Deg Days

°C

Total Rainmm

Total Snow

cm

Total Precip

mm

Snow on Grnd

cm

Dir of Max Gust

10's Deg


01 18.3 9.2 13.8 4.2 0.0 0.0 0.0 0.0 0 29 44 02 24.8 6.8 15.8 2.2 0.0 0.0 0.0 0.0 0 22 39 03 17.8 10.2 14.0 4.0 0.0 10.0 0.0 10.0 0 <31 04 14.0 10.2 12.1 5.9 0.0 T 0.0 T 0 5 46 05 21.9 12.0 17.0 1.0 0.0 1.4 0.0 1.4 0 <31 06 31.0 21.0 26.0 0.0 8.0 0.0 0.0 0.0 0 23 54 07 28.6 21.0 24.8 0.0 6.8 0.0 0.0 0.0 0 24 41 08 31.0 19.1 25.1 0.0 7.1 11.6 0.0 11.6 0 23 56 09 30.7 17.5 24.1 0.0 6.1 6.4 0.0 6.4 0 23 70 10 22.7 14.3 18.5 0.0 0.5 2.6 0.0 2.6 0 23 54 11 26.8 12.3 19.6 0.0 1.6 0.0 0.0 0.0 0 31 37 12 18.6 13.5 16.1 1.9 0.0 T 0.0 T 0 7 43 13 29.3 13.4 21.4 0.0 3.4 21.0 0.0 21.0 0 24 59 14 25.9 14.8 20.4 0.0 2.4 0.4 0.0 0.4 0 29 32 15 26.2 13.0 19.6 0.0 1.6 25.0 0.0 25.0 0 3 56 16 24.6 13.2 18.9 0.0 0.9 T 0.0 T 0 34 48 17 17.3 9.0 13.2 4.8 0.0 4.6 0.0 4.6 0 28 46 18 18.1 9.5 13.8 4.2 0.0 1.2 0.0 1.2 0 32 32 19 17.6 9.0 13.3 4.7 0.0 1.8 0.0 1.8 0 <31 20 23.5 12.1 17.8 0.2 0.0 0.0 0.0 0.0 0 <31 21 23.9 11.8 17.9 0.1 0.0 1.2 0.0 1.2 0 25 37 22 24.0 13.5 18.8 0.0 0.8 0.2 0.0 0.2 0 23 33 23 22.6 12.6 17.6 0.4 0.0 T 0.0 T 0 <31 24 24.7 12.0 18.4 0.0 0.4 0.0 0.0 0.0 0 <31 25 26.5 11.7 19.1 0.0 1.1 T 0.0 T 0 25 44 26 27.3 18.3 22.8 0.0 4.8 T 0.0 T 0 25 41 27 28.7 16.6 22.7 0.0 4.7 6.8 0.0 6.8 0 <31 28 25.2 19.3 22.3 0.0 4.3 8.0 0.0 8.0 0 24 39 29 24.0 12.9 18.5 0.0 0.5 1.2 0.0 1.2 0 25 35 30 23.0 11.8 17.4 0.6 0.0 0.0 0.0 0.0 0 <31 Sum 34.2 55.0 103.4 0.0 103.4 Avg 24.0 13.4 18.7 Xtrm 31.0S 6.8 23 70



Daily Data Report for July 2008

D a y

Max Temp

°C

Min Temp

°C

Mean Temp

°C

Heat Deg Days

°C

Cool Deg Days

°C

Total Rainmm

Total Snow

cm

Total Precip

mm

Snow on Grnd

cm

Dir of Max Gust

10's Deg


01 24.5 10.7 17.6 0.4 0.0 0.0 0.0 0.0 0 <31 02 26.8 12.4 19.6 0.0 1.6 T 0.0 T 0 22 52 03 23.1 10.5 16.8 1.2 0.0 1.6 0.0 1.6 0 23 37 04 22.9 8.9 15.9 2.1 0.0 0.0 0.0 0.0 0 <31 05 26.2 11.2 18.7 0.0 0.7 0.0 0.0 0.0 0 <31 06 28.6 13.3 21.0 0.0 3.0 0.0 0.0 0.0 0 <31 07 29.3 13.8 21.6 0.0 3.6 0.0 0.0 0.0 0 19 33 08 29.5 19.6 24.6 0.0 6.6 T 0.0 T 0 22 41 09 28.4 14.3 21.4 0.0 3.4 T 0.0 T 0 28 43 10 27.0 10.5 18.8 0.0 0.8 0.0 0.0 0.0 0 29 32 11 24.2 16.7 20.5 0.0 2.5 10.2 0.0 10.2 0 <31 12 29.2 17.7 23.5 0.0 5.5 3.8 0.0 3.8 0 24 52 13 27.5 14.2 20.9 0.0 2.9 0.8 0.0 0.8 0 24 41 14 24.9 13.0 19.0 0.0 1.0 0.0 0.0 0.0 0 28 44 15 26.3 11.3 18.8 0.0 0.8 0.0 0.0 0.0 0 <31 16 31.7 14.6 23.2 0.0 5.2 0.8 0.0 0.8 0 17 33 17 31.3 19.6 25.5 0.0 7.5 0.4 0.0 0.4 0 <31 18 29.3 19.5 24.4 0.0 6.4 T 0.0 T 0 23 37 19 29.2 19.4 24.3 0.0 6.3 24.4 0.0 24.4 0 24 33 20 21.7 18.6 20.2 0.0 2.2 14.4 0.0 14.4 0 <31 21 25.9 16.0 21.0 0.0 3.0 22.0 0.0 22.0 0 34 70 22 24.6 15.6 20.1 0.0 2.1 34.8 0.0 34.8 0 <31 23 22.0 15.0 18.5 0.0 0.5 4.2 0.0 4.2 0 2 41 24 25.5 14.2 19.9 0.0 1.9 0.0 0.0 0.0 0 <31 25 27.1 13.3 20.2 0.0 2.2 0.0 0.0 0.0 0 22 35 26 26.1 14.2 20.2 0.0 2.2 17.0 0.0 17.0 0 28 41 27 26.3 11.9 19.1 0.0 1.1 4.4 0.0 4.4 0 30 44 28 27.6 16.0 21.8 0.0 3.8 0.0 0.0 0.0 0 <31 29 27.5 12.9 20.2 0.0 2.2 0.0 0.0 0.0 0 <31 30 26.1 19.6 22.9 0.0 4.9 9.8 0.0 9.8 0 25 48 31 27.6 15.9 21.8 0.0 3.8 0.0 0.0 0.0 0 25 33 Sum 3.7 87.7 148.6 0.0 148.6 Avg 26.7 14.7 20.7 Xtrm 31.7 8.9 34 70



Daily Data Report for August 2008

D a y

Max Temp

°C

Min Temp

°C

Mean Temp

°C

Heat Deg Days

°C

Cool Deg Days

°C

Total Rainmm

Total Snow

cm

Total Precip

mm

Snow on Grnd

cm

Dir of Max Gust

10's Deg


01 27.0 15.0 21.0 0.0 3.0 T 0.0 T 0 <31 02 25.9 15.7 20.8 0.0 2.8 6.6 0.0 6.6 0 <31 03 26.3 14.2 20.3 0.0 2.3 0.0 0.0 0.0 0 <31 04 26.2 13.1 19.7 0.0 1.7 0.0 0.0 0.0 0 <31 05 27.3 18.1 22.7 0.0 4.7 12.0 0.0 12.0 0 <31 06 26.9 17.4 22.2 0.0 4.2 0.0 0.0 0.0 0 <31 07 24.8 14.5 19.7 0.0 1.7 5.2 0.0 5.2 0 <31 08 23.3 12.7 18.0 0.0 0.0 T 0.0 T 0 32 43 09 23.0 10.9 17.0 1.0 0.0 37.2 0.0 37.2 0 19 46 10 16.4 9.8 13.1 4.9 0.0 12.0 0.0 12.0 0 <31 11 24.1 9.9 17.0 1.0 0.0 0.0 0.0 0.0 0 <31 12 24.2 11.8 18.0 0.0 0.0 1.2 0.0 1.2 0 <31 13 22.6 12.4 17.5 0.5 0.0 4.4 0.0 4.4 0 35 37 14 24.1 11.8 18.0 0.0 0.0 4.6 0.0 4.6 0 35 37 15 23.3 10.6 17.0 1.0 0.0 1.4 0.0 1.4 0 <31 16 24.5 12.7 18.6 0.0 0.6 0.0 0.0 0.0 0 27 35 17 26.5 14.2 20.4 0.0 2.4 0.0 0.0 0.0 0 <31 18 27.9 16.4 22.2 0.0 4.2 16.2 0.0 16.2 0 22 33 19 20.6 11.6 16.1 1.9 0.0 T 0.0 T 0 <31 20 21.4 9.4 15.4 2.6 0.0 0.0 0.0 0.0 0 <31 21 23.3 12.2 17.8 0.2 0.0 0.0 0.0 0.0 0 <31 22 28.4 16.0 22.2 0.0 4.2 0.0 0.0 0.0 0 <31 23 27.3 17.7 22.5 0.0 4.5 0.0 0.0 0.0 0 <31 24 27.4 12.9 20.2 0.0 2.2 5.8 0.0 5.8 0 <31 25 20.6 11.4 16.0 2.0 0.0 0.0 0.0 0.0 0 <31 26 20.4 9.5 15.0 3.0 0.0 0.0 0.0 0.0 0 <31 27 20.3 11.4 15.9 2.1 0.0 0.0 0.0 0.0 0 <31 28 21.9 15.9 18.9 0.0 0.9 1.8 0.0 1.8 0 16 37 29 24.5 16.9 20.7 0.0 2.7 T 0.0 T 0 <31 30 26.4 13.2 19.8 0.0 1.8 0.0 0.0 0.0 0 <31 31 27.1 11.4 19.3 0.0 1.3 0.0 0.0 0.0 0 <31 Sum 20.2 45.2 108.4 0.0 108.4 Avg 24.3 13.2 18.8 Xtrm 28.4 9.4 19 46



Daily Data Report for September 2008

D a y

Max Temp

°C

Min Temp

°C

Mean Temp

°C

Heat Deg Days

°C

Cool Deg Days

°C

Total Rainmm

Total Snow

cm

Total Precip

mm

Snow on Grnd

cm

Dir of Max Gust

10's Deg


01 27.1 13.2 20.2 0.0 2.2 0.0 0.0 0.0 0 <31 02 27.6 13.6 20.6 0.0 2.6 0.0 0.0 0.0 0 <31 03 28.5 12.8 20.7 0.0 2.7 T 0.0 T 0 <31 04 25.0 15.7 20.4 0.0 2.4 0.0 0.0 0.0 0 <31 05 24.9 16.1 20.5 0.0 2.5 1.8 0.0 1.8 0 22 82 06 20.7 11.5 16.1 1.9 0.0 6.2 0.0 6.2 0 <31 07 18.8 9.5 14.2 3.8 0.0 24.8 0.0 24.8 0 <31 08 22.9 9.2 16.1 1.9 0.0 0.6 0.0 0.6 0 <31 09 20.0 8.6 14.3 3.7 0.0 12.6 0.0 12.6 0 <31 10 17.8 7.2 12.5 5.5 0.0 0.0 0.0 0.0 0 <31 11 20.2 8.3 14.3 3.7 0.0 0.0 0.0 0.0 0 <31 12 21.8 12.3 17.1 0.9 0.0 19.1 0.0 19.1 0 <31 13 23.4 19.0 21.2 0.0 3.2 19.0 0.0 19.0 0 22 50 14 27.7 17.3 22.5 0.0 4.5 9.8 0.0 9.8 0 22 80 15 18.1 7.8 13.0 5.0 0.0 1.6 0.0 1.6 0 <31 16 18.1 5.2 11.7 6.3 0.0 0.0 0.0 0.0 0 <31 17 23.4 7.6 15.5 2.5 0.0 0.0 0.0 0.0 0 23 35 18 17.9 9.3 13.6 4.4 0.0 0.0 0.0 0.0 0 <31 19 21.1 7.4 14.3 3.7 0.0 0.0 0.0 0.0 0 <31 20 24.9 11.4 18.2 0.0 0.2 0.0 0.0 0.0 0 <31 21 17.8 9.6 13.7 4.3 0.0 0.0 0.0 0.0 0 <31 22 17.2 8.5 12.9 5.1 0.0 0.0 0.0 0.0 0 <31 23 19.0 9.1 14.1 3.9 0.0 0.0 0.0 0.0 0 <31 24 24.4 9.9 17.2 0.8 0.0 0.0 0.0 0.0 0 <31 25 24.3 10.4 17.4 0.6 0.0 0.0 0.0 0.0 0 <31 26 18.6 13.0 15.8 2.2 0.0 T 0.0 T 0 4 43 27 17.7 15.2 16.5 1.5 0.0 0.8 0.0 0.8 0 <31 28 22.1 13.5 17.8 0.2 0.0 0.2 0.0 0.2 0 35 35 29 13.9 11.3 12.6 5.4 0.0 T 0.0 T 0 <31 30 18.9 10.9 14.9 3.1 0.0 12.6 0.0 12.6 0 <31 Sum 70.4 20.3 109.1 0.0 109.1 Avg 21.5 11.1 16.3 Xtrm 28.5 5.2 22 82



Appendix II: MOE Analytical Methods 82 PCB congeners analyzed through MOE method PCBC3459 (water): Test Code PCB Congener name PCBTOT PCB CONGENER TOTAL PCX001 2-MONOCHLOROPCB(1) PCX003 4-MONOCHLOROPCB(3) PCX006 2,3'-DICHLOROPCB(6) PCX008 2,4'-DICHLOROPCB(8) PCX015 4,4'-DICHLOROPCB(15) PCX016 2,2',3-TRICHLOROPCB(16) PCX018 2,2',5-TRICHLOROPCB(18) PCX019 2,2',6-TRICHLOROPCB(19) PCX022 2,3,4'-TRICHLOROPCB(22) PCX031 2,4',5-TRICHLOROPCB(31) PCX037 3,4,4'-TRICHLOROPCB(37) PCX040 2,2',3,3'-TETRACHLOROPCB(40) PCX041 2,2',3,4-TETRACHLOROPCB(41) PCX044 2,2',3,5'-TETRACHLOROPCB(44) PCX049 2,2',4,5'-TETRACHLOROPCB(49) PCX052 2,2',5,5'-TETRACHLOROPCB(52) PCX054 2,2',6,6'-TETRACHLOROPCB(54) PCX060 2,3,4,4'-TETRACHLOROPCB(60) PCX066 2,3',4,4'-TETRACHLOROPCB(66) PCX070 2,3',4',5-TETRACHLOROPCB(70) PCX074 2,4,4',5-TETRACHLOROPCB(74) PCX077 3,3',4,4'-TETRACHLOROPCB(77) PCX081 3,4,4',5-TETRACHLOROPCB(81) PCX084 PECLPCB(84)+(90)+(101) PCX085 2,2',3,4,4'-PENTACHLOROPCB(85) PCX087 2,2',3,4,5'-PENTACHLOROPCB(87) PCX095 2,2',3,5',6-PENTACHLOROPCB(95) PCX097 2,2',3',4,5-PENTACHLOROPCB(97) PCX099 2,2',4,4',5-PENTACHLOROPCB(99) PCX104 2,2',4,6,6'-PENTACHLOROPCB(104) PCX105 2,3,3',4,4'-PENTACHLOROPCB(105) PCX110 2,3,3',4',6-PENTACHLOROPCB(110) PCX114 2,3,4,4',5-PENTACHLOROPCB(114) PCX118 2,3',4,4',5-PENTACHLOROPCB(118) PCX119 2,3',4,4',6-PENTACHLOROPCB(119) PCX123 2',3,4,4',5-PENTACHLOROPCB(123) PCX126 3,3',4,4',5-PENTACHLOROPCB(126) PCX128 2,2',3,3',4,4'-HEXACHLOROPCB(128) PCX135 2,2',3,3',5,6'-HEXACHLPCB(135) PCX137 2,2',3,4,4',5-HEXACHLOROPCB(137)



PCX138 2,2',3,4,4',5'-HEXACHLOROPCB(138) PCX141 2,2',3,4,5,5'-HEXACHLOROPCB(141) PCX149 2,2',3,4',5',6-HEXACHLOROPCB(149) PCX151 2,2',3,5,5',6-HEXACHLOROPCB(151) PCX155 2,2',4,4',6,6'-HEXACHLOROPCB(155) PCX156 2,3,3',4,4',5-HEXACHLOROPCB(156) PCX157 2,3,3',4,4',5'-HEXACHLOROPCB(157) PCX158 22'33'45(129)+233'44'6-HXCLPCB (158) PCX167 2,3',4,4',5,5'-HEXACHLOROPCB(167) PCX168 22'44'55'(153)+23'44'5'6-HXCLPCB (168) PCX169 3,3',4,4',5,5'-HEXACHLOROPCB(169) PCX170 2,2',3,3',4,4',5-HEPTACHLOROPCB (170) PCX171 2,2',3,3',4,4',6-HEPTACHLOROPCB (171) PCX174 2,2',3,3',4,5,6'-HEPPCB(174) PCX177 2,2',3,3',4',5,6-HEPTACHLOROPCB (177) PCX178 2,2',3,3',5,5',6-HEPTACHLOROPCB (178) PCX183 2,2',3,4,4',5',6-HEPTACHLOROPCB (183) PCX187 2,2',3,4',5,5',6-HEPTACHLOROPCB (187) PCX188 2,2',3,4',5,6,6'-HEPTACHLOROPCB (188) PCX189 2,3,3',4,4',5,5'-HEPTACHLOROPCB (189) PCX191 2,3,3',4,4',5',6-HEPTACHLOROPCB (191) PCX193 22'344'55'(180)+233'4'55'6-HPCLPCB (193) PCX194 2,2',3,3',4,4',5,5'-OCTACHLOROPCB (194) PCX199 2,2',3,3',4,5,5',6'-OCTACHLOROPCB (199) PCX200 2,2',3,3',4,5,6,6'-OCTPCB(200) PCX201 2,2',3,3',4,5',6,6'-OCTACHLOROPCB (201) PCX202 2,2',3,3',5,5',6,6'-OCTACHLOROPCB (202) PCX203 2,2',3,4,4',5,5',6-OCTACHLOROPCB (203) PCX205 2,3,3',4,4',5,5',6-OCTACHLOROPCB (205) PCX206 22'33'44'55'6-NONACHLOROPCB(206) PCX207 22'33'44'566'-NONACHLPCB(207) PCX208 22'33'455'66'-NONACHLOROPCB(208) PCX209 DECACHLOROPCB(209) PCX233 244'-TRICLPCB(28)+2'34-TRICLPCB (33) PCX410 2,2'-DICHLOROPCB(4)+2,6-DICHLPCB (10) 55 PCB congeners analyzed through MOE method PCB3412 (sediment): Test Code PCB Congener Name PCB018 2,2',5-TRICHLOROBIPHENYL PCB019 2,2',6-TRI(CL)BIPHENYL PCB022 2,3,4'-TRICHLOROBIPHENYL PCB028 2,4,4'-TRICHLOROBIPHENYL PCB033 2',3,4-TRICHLOROBIPHENYL PCB037 3,4,4'-TRICHLOROBIPHENYL PCB044 2,2',3,5'-TETRACHLOROBIPHENYL



PCB049 2,2',4,5'-TETRACHLOROBIPHENYL PCB052 2,2',5,5'-TETRACHLOROBIPHENYL PCB054 2,2',6,6'-TETRA(CL)BIPHENYL PCB070 2,3',4',5-TETRACHLOROBIPHENYL PCB074 2,4,4',5-TETRACHLOROBIPHENYL PCB077 3,3',4,4'-TETRACHLOROBIPHENYL PCB081 3,4,4',5-TETRACHLOROBIPHENYL PCB087 2,2'3,4,5'-PENTACHLOROBIPHENYL PCB095 2,2'3,5',6-PENTACHLOROBIPHENYL PCB099 2,2'4,4',5-PENTACHLOROBIPHENYL PCB101 2,2'4,5,5'-PENTACHLOROBIPHENYL PCB104 2,2'4,6,6'-PENTA(CL)BIPHENYL PCB105 2,3,3'4,4'-PENTACHLOROBIPHENYL PCB110 2,3,3'4',6-PENTACHLOROBIPHENYL PCB114 2,2'3,4,5'-PENTACHLOROBIPHENYL PCB118 2,3'4,4',5-PENTACHLOROBIPHENYL PCB119 2,3'4,4',6-PENTACHLOROBIPHENYL PCB123 2'3,4,4',5-PENTA(CL)BIPHENYL PCB126 3,3'4,4',5-PENTACHLOROBIPHENYL PCB128 22',33',44'-HEXA(CL)BIPHENYL PCB138 2,2'3,44'5'-HEXACHLOROBIPHENYL PCB149 2,2'3,3'46'-HEXACHLOROBIPHENYL PCB151 2,2'3,5,5'6-HEXA(CL)BIPHENYL PCB153 22',44',55'-HEXACHLOROBIPHENYL PCB155 22',44',66'-HEXA(CL)BIPHENYL PCB156 2,3,3'4,4'5-HEXACHLOROBIPHENYL PCB157 2,3,3'44'5'-HEXACHLOROBIPHENYL PCB158 2,3,3'4,4'6-HEXACHLOROBIPHENYL PCB167 23',44',55'-HEXA(CL)BIPHENYL PCB168 23',44',5'6-HEXA(CL)BIPHENYL PCB169 3,3'4,4'55'-HEXACHLOROBIPHENYL PCB170 22'33'44'5-HEPTA(CL)BIPHENYL PCB171 22'33'44'6-HEPTA(CL)BIPHENYL PCB177 22'33'4'56-HEPTA(CL)BIPHENYL PCB178 22'33'55'6-HEPTA(CL)BIPHENYL PCB180 22'344'55'-HEPTACHLOROBIPHENYL PCB183 22'344'5'6-HEPTA(CL)BIPHENYL PCB187 22'34'55'6-HEPTA(CL)BIPHENYL PCB188 22'34'566'-HEPTA(CL)BIPHENYL PCB189 233'44'55'-HEPTA(CL)BIPHENYL PCB191 233'44'5'6-HEPTACHLOROBIPHENYL PCB194 22'33'44'55'-OCTACHLOBIPHENYL PCB199 22'33'455'6'-OCTA(CL)BIPHENYL PCB201 22'33'45'66'-OCTA(CL)BIPHENYL PCB202 22'33'55'66'-OCTA(CL)BIPHENYL PCB205 233'44'55'6-OCTACHLOBIPHENYL PCB206 22'33'44'55'6-OCTACHLOBIPHENYL PCB208 22'33'455'66'NONA(CL)BIPHENYL



18 PAH compounds analyzed through MOE method PAH3425 (sediment): Test Code PAH Compound Name PNACNE ACENAPHTHENE PNACNY ACENAPHTHYLENE PNANTH ANTHRACENE PNBAA BENZO(A)ANTHRACENE PNBAP BENZO(A)PYRENE PNBBFA BENZO (B) FLUORANTHENE PNBEP BENZO(E)PYRENE PNBKF BENZO (K) FLUORANTHENE PNCHRY CHRYSENE PNDAHA DIBENZO(AH)ANTHRACENE PNFLAN FLUORANTHENE PNFLUO FLUORENE PNGHIP BENZO(G,H,I) PERYLENE PNINP INDENO(1,2,3-CD) PYRENE PNNAPH NAPHTHALENE PNPERY PERYLENE PNPHEN PHENANTHRENE PNPYR PYRENE



Appendix III: Semi-Permeable Membrane Device (SPMD) Background and Methods

Prepared by:

Chris D. Metcalfe and Tracy L. Metcalfe Environmental and Resource Studies

Trent University Peterborough, ON

May 5, 2008

Introduction

At the request of the Ontario Ministry of Environment (OME), Trent University proposes to utilize semi-permeable membrane devices (SPMDs) to monitor the concentrations of PCBs in the surface water of Hamilton Harbour. SPMDs are simple and economical devices for monitoring the distribution of hydrophobic organic contaminants that are present in water at part per billion (i.e. ug/L) or part per trillion (i.e. ng/L) concentrations; levels that would be difficult to detect using conventional extraction techniques. The SPMD is a porous polymeric membrane that contains a thin film of triolein, a synthetic lipid compound (Huckins et al., 1997). Once the SPMD is deployed, hydrophobic organic contaminants pass from the aqueous phase through the polyethylene and are concentrated in the triolein. When the device is retrieved, usually one month after deployment, these compounds can be extracted from the triolein for isolation, concentrations and analysis. The SPMDs sample only the contaminants that are in the dissolved phase of the surrounding medium. Any compounds adsorbed to suspended particulates or colloids will not pass through the polymer membrane into the triolein. These devices are inexpensive, robust and have given good results in previous monitoring studies for PCBs (Bennett et al., 1996, Metcalfe et al., 2000, O’Toole et al., 2006). Proposal

All work will be conducted as a contract to Trent University under the supervision of Prof. Chris Metcalfe of the Environmental and Resource Studies Program. The work will consist of preparation of SPMDs prior to deployment, provision of cleaned and prepared shrouds, and after retrieval, preparation of extracts, followed by isolation, concentration and analysis of PCBs on a congener specific basis. OME will arrange for pick-up and return of SPMDs from Trent under refrigerated conditions. OME will deploy and retrieve SPMDs from the sampling sites.

Trent University will prepare 45 SPMDs from polyethylene strips containing one mL of 95% triolein (Sigma, Toronto). The SPMDs will be placed in solvent washed jars and frozen at –100C. Galvanized metal shrouds and hardware for deploying 3 replicate SPMDs will also be prepared and provided by Trent University. “Trip blank” SPMDs will also be provided at the rate of one trip blank for each deployment site. After retrieval,



each SPMD will be cleaned and the contaminants dialyzed into hexane. Residual triolein will be removed from the dialysate by gel permeation chromatography (GPC), and the extract will be fractionated by silica gel column chromatography as described previously (Metcalfe et al., 2000). Sulphur contamination will be removed by addition of copper foil to the sample following extraction, and additionally with copper powder following silica gel clean up.

The PCB fraction isolated by column chromatography will be analyzed for PCB congeners by gas chromatography with an electron capture detector (GC-ECD). Analytical data will be provided to OME in an Excel spreadsheet with data on concentrations of individual PCB concentrations expressed as ng/mL of triolein. Total PCBs will also be calculated for each SPMD. Qualifications of Trent University:

The laboratory at Trent University is uniquely qualified in Canada to conduct this work. Individuals working under the supervision of Chris and Tracy Metcalfe started working with SPMDs in 1994 and have published several peer-reviewed manuscripts that describe monitoring studies with this technique. The Trent laboratory is the only research group in Canada that prepares its own SPMDs for deployment. All methods for the preparation of SPMD samples for PCB analysis have been verified.

The Trent laboratory has been involved in congener-specific analysis of PCBs in environmental samples since 1986, and has participated in several intra-laboratory round robins involving analysis of PCBs in various samples matrices (e.g. sediments, fish, and marine mammals). All sample preparation procedures and analytical techniques have been verified by intra-laboratory comparisons and analysis of standard reference materials. Individuals working in the Trent laboratory have published over 40 peer-reviewed manuscripts and one book chapter dealing with the analysis of PCBs in environmental matrices. Literature Cited Bennett ER, Metcalfe TL, Metcalfe CD. 1997. Semi-permeable membrane devices

(SPMDs) for monitoring organic contaminants in the Otonabee River, Ontario. Chemosphere 33:363-375.

Huckins JN, Petty JD, Lebo JA, Orazio CE, Prest HF, Tillit DE, Ellis GS, Johnson BT,

Mauweera GK, 1997. Semipermeable membrane devices (SPMDs) for the concentration and assessment of bioavailable organic contaminants in aquatic environments. In: Techniques in Aquatic Toxicology, G Ostrander (Ed), Lewis Publishers, Boca Raton, FL, USA, pp 625-655.

Metcalfe TL, Metcalfe CD, Bennett ER, Haffner D. 2000. Distribution of toxic organic

contaminants in water and sediments in the Detroit River. J Great Lakes Res. 26:55-64.



O'Toole S, Metcalfe CD, Crane I, Gross M. 2006. Release of persistent organic contaminants from carcasses of Lake Ontario Chinook salmon (Oncorhynchus tshawytscha). Environmental Pollution 140: 99-110.



Appendix IV: Water Column Profiles and Sampling Depths at Nine Stations for Five Water Quality Surveys Reader should also note that data on conductivity, pH and Secchi Disc Depth were also collected but data are not shown.

-24-22-20-18-16-14-12-10

-8-6-4-20

-5 0 5 10 15 20Station 258 - May 28, 2008

Dep

th b

elow

sur

face

(m)

Turbidity (NTU)Temperature (C)

Bottom grab = 21.5 m depth

Surface-integrated sample =surface - 21.5 m depth

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Station 268 - May 28, 2008

Dep

th b

elow

sur

face

(m)




-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

0-5 0 5 10 15 20

Station 352 - May 28, 2008

Dep

th b

elow

sur

face

(m)




-14

-12

-10

-8

-6

-4

-2

0-5 0 5 10 15 20

Station 365 - May 28, 2008

Dep

th b

elow

sur

face

(m)






-9

-8

-7

-6

-5

-4

-3

-2

-1

0-5 0 5 10 15 20

Station 366 - May 28, 2008D

epth

bel

ow s

urfa

ce (m

)




-6

-5

-4

-3

-2

-1

0-5 0 5 10 15 20

Station 367 - May 28, 2008

Dep

th b

elow

sur

face

(m)




-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 100 200 300 400 500 600

Station 368 - May 28, 2008

Dep

th b

elow

sur

face

(m)




-9

-8

-7

-6

-5

-4

-3

-2

-1

0-5 0 5 10 15 20 25

Station 369 - May 28, 2008

Dep

th b

elow

sur

face

(m)






-12

-10

-8

-6

-4

-2

0-5 0 5 10 15 20

Station 370 - May 28, 2008D

epth

bel

ow s

urfa

ce (m

)




-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20

Station 372 - May 28, 2008

Dep

th b

elow

sur

face

(m)





-25

-20

-15

-10

-5

00 5 10 15 20

Dep

th b

elow

sur

face

(m)

Turbidity (FTU)Temperature (C)DO (mg/L)


Surface-integrated sample = surface - 10.5 m depth


-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20

Dep

th b

elow

sur

face

(m)







-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25 30

Dep

th b

elow

sur

face

(m)





-14

-12

-10

-8

-6

-4

-2

00 5 10 15 20

Dep

th b

elow

sur

face

(m)

Turbidity (FTU)Temperature (C)DO (mg/L)Bottom grab = 13.5 m depth



-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20

Dep

th b

elow

sur

face

(m) Turbidity (FTU)

Temperature (C)DO (mg/L)




-6

-5

-4

-3

-2

-1

00 5 10 15 20

Dep

th b

elow

sur

face

(m)







-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20

Dep

th b

elow

sur

face

(m) Turbidity (FTU)

Temperature (C)DO (mg/L)




-6

-5

-4

-3

-2

-1

00 5 10 15 20

Dep

th b

elow

sur

face

(m)





-12

-10

-8

-6

-4

-2

00 5 10 15 20

Dep

th b

elow

sur

face

(m)







-25

-20

-15

-10

-5

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25 30

Dep

th b

elow

sur

face

(m)





-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-16

-14

-12

-10

-8

-6

-4

-2

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)


Bottom grab = 14.0 m





-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)

Turbidity (FTU)Temperature (C)DO (mg/L)Bottom grab = 9.0 m depth



-9

-8

-7

-6

-5

-4

-3

-2

-1

00 10 20 30 40

Dep

th b

elow

sur

face

(m)







-14

-12

-10

-8

-6

-4

-2

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-25

-20

-15

-10

-5

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-8

-7

-6

-5

-4

-3

-2

-1

00 10 20 30 40 50 60

Dep

th b

elow

sur

face

(m)







-9

-8

-7

-6

-5

-4

-3

-2

-1

00 10 20 30 40 50 60 70

Dep

th b

elow

sur

face

(m)





-14

-12

-10

-8

-6

-4

-2

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-6

-5

-4

-3

-2

-1

00 20 40 60 80 100 120

Dep

th b

elow

sur

face

(m)







-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25 30

Dep

th b

elow

sur

face

(m)





-12

-10

-8

-6

-4

-2

00 10 20 30 40 50 60 70

Dep

th b

elow

sur

face

(m)







-25

-20

-15

-10

-5

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)

Turbidity (FTU)TemperatureDO (mg/L)




-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25 30

Dep

th b

elow

sur

face

(m)





-16

-14

-12

-10

-8

-6

-4

-2

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)







-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-6

-5

-4

-3

-2

-1

00 5 10 15 20

Dep

th b

elow

sur

face

(m)





-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)





-8

-7

-6

-5

-4

-3

-2

-1

00 20 40 60 80 100

Dep

th b

elow

sur

face

(m)







-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

00 5 10 15 20 25

Dep

th b

elow

sur

face

(m)



Bottom grab = 10.0 m



Appendix V: Qualitative field notes on condition of metal shrouds and external surface of SPMDs upon retrieval Station Notes for July 2, 2008 retrieval: 0258 Shroud covered in rust (red) 0268 Shroud: covered in red slime with brown goo streaming off; SPMDs

covered in brown goo 0352 Shroud – very little algae; SPMDs – brown goo on it 0365 Shroud had very little algae; SPMDs had some algae on them 0366 Shroud covered in red rust goo; SPMDs relatively clean with snails on

them 0367 Shroud & SPMDs covered in some algae (brown/green) 0368 Shroud & SPMDs covered in algae (brown/green) 0369 Shroud & SPMDs covered in brown goo 0370 Shroud had some algae; SPMDs – lots of algae 0371* SPMDs covered in brown mud; shroud had some corrosion & algae *retrieved July 3, 2008 Station Notes for September 17, 2008 retrieval: 0258 No rust on shroud; a little algae; some zebra/quagga? mussels

attached to bottom of Viny float upon retrieval. Also, many good-sized mussels attached to buoy. Lots of orange/red stringy algae attached to buoy cable. Algae was green close to surface near part attached to buoy and red/orange on cable a bit deeper; many feet (10?) of cable with algae attached .

0268 Shroud covered in rusty coloured slime. 0352 Shroud was very clean but finish was altered; was a matte grey colour

(not shiny). No obvious algae, except some on Viny float. 0365 A bit of algae on bottom of Viny float and shroud. 0366 Shroud was dark grey and black specs and some brown slime. Some

oil/sheen on shroud. Some mussels and segmented worms (crawling) on shroud. Blue-green algae on top part of shroud and also some stuck to end of SPMD where folded over.

0367 Shroud very clean; metal still shiny. SPMDs had little tubes/algae strings (?) on them. Some algae on bottom of Viny float.

0368 Shroud relatively clean – some of the original metal shininess still visible (not tarnished). Viny float cleaner relative to stn 258.

0369 Brown slime and worms on shroud; SPMDs a little ‘gooier’ than the other stations.

0370 Shroud had very little fouling – no rust; next to no algae 0371* SPMDs very muddy! Possibly laying on sediment surface due to water

level drop. *retrieved September 18, 2008



Appendix VI: Tidbit Temperature Data for Ten Stations and Two SPMD Deployments

Temperature at Station 258 (Centre station) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)

Temperature at Station 268 (Windermere Arm/Basin Bridge) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)

Temperature at Station 352 (Centre of Windermere Arm) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)

Temperature at Station 365 (near Randle Reef) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)



Temperature at Station 366 (Strathearne Slip) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)

Temperature at Station 367 (west end of Harbour) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)

Temperature at Station 368 (near LaSalle Marina) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)

Temperature at Station 369 (Dofasco boat slip) - June 2008

0

5

10

15

20

25

04/0

6/20

08

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)



Temperature at Station 370 (Windermere Arm mouth) - June 2008

0

5

10

15

20

2504

/06/

2008

06/0

6/20

08

08/0

6/20

08

10/0

6/20

08

12/0

6/20

08

14/0

6/20

08

16/0

6/20

08

18/0

6/20

08

20/0

6/20

08

22/0

6/20

08

24/0

6/20

08

26/0

6/20

08

28/0

6/20

08

30/0

6/20

08

Tem

pera

ture

(C)

Temperature at Station 371 (Cootes Paradise) - June 2008

0

5

10

15

20

25

30

05/0

6/20

08

07/0

6/20

08

09/0

6/20

08

11/0

6/20

08

13/0

6/20

08

15/0

6/20

08

17/0

6/20

08

19/0

6/20

08

21/0

6/20

08

23/0

6/20

08

25/0

6/20

08

27/0

6/20

08

29/0

6/20

08

01/0

7/20

08

Tem

pera

ture

(C)

Temperature at Station 258 (Centre station) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

Tem

pera

ture

(C)

Temperature at Station 268 (Windermere Arm/Basin Bridge) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

Tem

pera

ture

(C)



Temperature at Station 352 (Centre of Windermere Arm) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

17/0

9/20

08

Tem

pera

ture

(C)

Temperature at Station 365 (near Randle Reef) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

17/0

9/20

08

Tem

pera

ture

(C)

Temperature at Station 366 (Strathearne Slip) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

Tem

pera

ture

(C)

Temperature at Station 367 (West end of Harbour) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

17/0

9/20

08

Tem

pera

ture

(C)



Temperature at Station 368 (near LaSalle Marina) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

17/0

9/20

08

Tem

pera

ture

(C)

Temperature at Station 369 (Dofasco boat slip) - August 2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

Tem

pera

ture

(C)

Temperature at Station 370 (Windermere Arm mouth) - August

2008

0

5

10

15

20

25

30

20/0

8/20

08

22/0

8/20

08

24/0

8/20

08

26/0

8/20

08

28/0

8/20

08

30/0

8/20

08

01/0

9/20

08

03/0

9/20

08

05/0

9/20

08

07/0

9/20

08

09/0

9/20

08

11/0

9/20

08

13/0

9/20

08

15/0

9/20

08

Tem

pera

ture

(C)

Documents

Hamiltonharbourfieldseasonassessment,labencki,2008