1. Developing a Cumulative Effects Monitoring Program for the Saint John Harbour – Contaminants Karen Kidd and Angella Mercer Canadian Rivers Institute, UNB Saint John kiddk@unbsj.ca, amercer1@unbsj.ca

2. Main Objectives To work with SJH Environmental Monitoring Partnership to: Determine seasonal and annual variability of contaminants at reference sites – characterize baseline levels Determine level and extent of contamination at sites of concern Design optimal program for long term monitoring: –Location and number of reference and impacted sites –Methods (timing and frequency of sampling, sampling and analytical methods) –Thresholds for assessing change

3. Concentrations of Some Metals Highly Variable in Harbour – Example is Copper from report by Land & Sea Environmental Consultants

4. Canadian Water Network Monitoring Program – Contaminants in Sediments Phase 1 – Years 1 to 3 Objective is to characterize reference sites and establish baseline levels Samples to characterize variability at reference locations –What is the range of concentrations at reference sites? –What season is the best to sample in? –How much variability is there within sites across years?

5. 6 reference sites:● 3 sites in inner harbour (blue) ● 3 sites in outer harbour (green) (site 13 replaced site 5) Sampling Sites Aug & Oct 2011, Apr and Jun 2012 Year 1 – 6 reference sites, 4 sampling dates Years 2 & 3 – 6 reference sites, 1 (optimal) sampling date

6. Methods for Sediments – Phase I Field Surface sediment grabs at 6 reference sites 5-10/site –Same timing and sites as invertebrate collections –Sampled top 5 cm of sediments –Frozen until processed

7. Methods – Phases 1 & 2 Lab Analyses of Sediments Freeze dried Standard US EPA methods used for extraction, clean up and analyses of sediments for metals, PAHs and PCBs Analyses include certified reference materials, lab and machine blanks, and replicates Organic carbon and grain size measured in sediments Samples from first 4 dates are complete

8. Contaminants Focus on metals and PAHs, PCBs for October sediments Metals/Elements - sediments analyzed for aluminum, arsenic, cadmium, cobalt, copper, chromium, iron, lanthanum, lead, magnesium, manganese, mercury, nickel, phosphorous, rubidium, selenium, silver, strontium, sulphur, thallium, uranium, vanadium and zinc (CCME guidelines exist for ones underlined; bolded ones previously monitored) PAHs – sediments analyzed for 16 priority compounds (CCME guidelines exist for 12) PCBs – 38 individual congeners, October samples only (results not shown here)

9. Contaminant levels Sites reference level My site threshold effects level What are the exposures? Some information on contamination levels so my site can be put in perspective Some information on thresholds and reference levels

10. 0 100 200 300 400 Zinc in Sediments from the Inner Saint John Harbour, 2011-2012 Date and Site Zn (mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 CCME PEL=271 mg/kg CCME ISQG = 124 mg/kg Past Results: Inner = 9-442 mg/kg Outer = 23.6-440 mg/kg 3x SD p = 16.1-77.9 mg/kg Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01

11. 0 100 200 300 400 Zinc in Sediments from the Outer Saint John Harbour, 2011-2012 Date and Site Zn (mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 CCME PEL=271 mg/kg CCME ISQG = 124 mg/kg Past Results: Inner = 9-442 mg/kg Outer = 23.6-440 mg/kg 3x SD p = 16.1-77.9 mg/kg

12. 0 10 20 30 40 50 Arsenic in Sediments from the Inner Saint John Harbour, 2011-2012 Date and Site As (mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Past Results: Inner = 5.3-14.8 mg/kg Outer = 1.7-26.5 mg/kg CCME PEL=41.6 mg/kg CCME ISQG = 7.24 mg/kg 3x SD p = 2.0-11.3 mg/kg Site 02Site 03 Site 01

13. 0 10 20 30 40 50 Arsenic in Sediments from the Outer Saint John Harbour, 2011-2012 Date and Site As(mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 Past Results: Inner = 5.3-14.8 mg/kg Outer = 1.7-26.5 mg/kg CCME PEL=41.6 mg/kg CCME ISQG = 7.24 mg/kg 3x SD p = 2.0-11.3 mg/kg

14. 0 1 2 10 30 50 Total PAHs in Sediments from the Inner Saint John Harbour, 2011-2012 TPAHs(mg/kg) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01 Date and Site Past Results: Little River= 0.0-46.55 mg/kg 3x SD p = 0.0-0.59 mg/kg noaa SQuiRT PEL=16.7 mg/kg noaa SQuiRT Threshold=1.6 mg/kg

15. 0 1 2 10 30 50 Total PAHs in Sediments from the Outer Saint John Harbour, 2011-2012 TPAHs(mg/kg ) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 Date and Site Past Results: Little River= 0.0-46.55 mg/kg noaa SQuiRT PEL=16.7 mg/kg noaa SQuiRT Threshold=1.6 mg/kg 3x SD p = 0.0-0.59 mg/kg

16. Phase I - Summary of Results Reference Sites Metals concentrations typically well below guidelines (lead, cadmium, copper, zinc, mercury) –Arsenic exceeds ISQG at all inner harbour sites and one outer harbour site –Chromium exceeds ISQG mainly at inner harbour sites –Aluminum above NOAA guidelines at all sites Total PAHs also well below effects thresholds for all four dates Total PCBs ranged from 2.2 to 17.5 ng/g dw, many congeners below MDL (<0.2 ng/g), most sites well below ISQG of 21.5 ng/g

17. Next Steps – Phase I and II 3 standard deviations captured all variability at reference sites, used as threshold for change Power analysis (using 3 SD) showed: –n of 3/site sufficient for detecting changes Oct 2012 –Re-sampled 6 reference sites (n=8/site) –Sampled 3 potentially more contaminated sites (“hotspots”) Collected surface sediments from 4 reference and 3 contaminated sites for toxicity testing (EC Moncton for Bryce Pippy’s MSc; n=5/site)

18. Phase I and II - Sites for Oct 2012 Sampling

19. At the End of Year 2 Results will be –Presented to SJH EMP –Used to design sampling program for Year 3 Repeat sampling of reference sites from Years 1 and 2 Sample and characterize “hotspots” in Harbour Potential to expand to other key areas Year 3 - Final deliverable - optimal design of long term monitoring program for contaminants in Saint John Harbour

20. References for Past Results Bezanson and Kranck (1981) Chou (2000) Loring (1979, 1982) Parrott et al. (2001) Ray MacKnight (1984) Tay et al. (1997) Washburn & Gillis (1993) Yurick (1982)

21. 0 20 40 60 80 100 Copper in Sediments from the Inner Saint John Harbour, 2011-2012 Cu (mg/kg dw ) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Date and Site Past Results: Inner = 5.8-45.1 mg/kg Outer = 3.0-106 mg/kg CCME PEL=108 mg/kg CCME ISQG = 18.7 mg/kg 3x SD p = 0.0-16.3 mg/kg Site 02Site 03 Site 01

22. 0 20 40 60 80 100 Copper in Sediment from the Outer Saint John Harbour, 2011-2012 Date and Site Cu (mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 Past Results: Inner = 5.8-45.1 mg/kg Outer = 3.0-106 mg/kg CCME PEL=108 mg/kg CCME ISQG = 18.7 mg/kg 3x SD p = 0.0-16.3 mg/kg

23. 0 1 2 3 4 5 Cadmium in Sediments from the Inner Saint John Harbour, 2011-2012 Date and Site Cd (mg/kg dw) Past Results: Inner = 0-6.1 mg/kg Outer = 0-3.9 mg/kg CCME PEL=4.2 mg/kg CCME ISQG = 0.700 mg/kg 3x SD p = 0-0.23 mg/kg Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01

24. 0 1 2 3 4 5 Cadmium from Sediments in the Outer Saint John Harbour, 2011-2012 Date and Site Cd (mg/kg dw ) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 Past Results: Inner = 0-6.1 mg/kg Outer = 0-3.9 mg/kg CCME PEL=4.2 mg/kg CCME ISQG = 0.700 mg/kg 3x SD p = 0-0.23 mg/kg

25. 0 20 40 60 80 100 120 Lead in Sediments from the Inner Saint John Harbour, 2011-2012 Date and Site Pb(mg/kg dw) Past Results: Inner = 6.3-98.8 mg/kg Outer = 7.0-130 mg/kg CCME PEL=112 mg/kg CCME ISQG = 30.2 mg/kg 3x SD p = 2.9-15.2 mg/kg Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01

26. 0 20 40 60 80 100 120 Lead in Sediments from the Outer Saint John Harbour, 2011-2012 Date and Site Pb(mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 Past Results: Inner = 6.3-98.8 mg/kg Outer = 7.0-130 mg/kg CCME PEL=112 mg/kg CCME ISQG = 30.2 mg/kg 3x SD p = 2.9-15.2 mg/kg

27. 0 50 100 150 Chromium in Sediments in the Inner Saint John Harbour, 2011-2012 Date and Site Cr(mg/kg dw) CCME PEL=160 mg/kg CCME ISQG = 30.2 mg/kg Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01 3x SD p = 8.7-42.8 mg/kg

28. 0 50 100 150 Chromium in Sediments for the Outer Saint John Harbour, 2011-2012 Date and Site Cr(mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 CCME PEL=160 mg/kg CCME ISQG = 30.2 mg/kg 3x SD p = 8.7-42.8 mg/kg

29. 0 100 200 300 400 500 600 700 Mercury in Sediments from the Inner Saint John Harbour, 2011-2012 Date and Site THg(ug/kg dw) CCME PEL=700 ug/kg CCME ISQG = 130 ug/kg Past Results: Inner = 0.0-330 ug/kg Outer = 0.0-610 ug/kg 3x SD p = 0.0-24.0 ug/kg Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01

30. 0 100 200 300 400 500 600 700 Mercury in Sediments from the Outer Saint John Harbour, 2011-2012 Date and Site THg (ug/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 CCME PEL=700 ug/kg CCME ISQG = 130 ug/kg Past Results: Inner = 0.0-330 ug/kg Outer = 0.0-610 ug/kg 3x SD p = 0.0-24.0 ug/kg

31. 0 5 10 15 20 25 Loss on Ignition 550 in Sediments from the Inner Saint John Harbour, 2011-2012 Date and Site LOI550(%) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01 3x SD p = 0.0-6.23%

32. 0 5 10 15 20 25 Loss on Ignition 550 in Sediments from the Outer Saint John Harbour, 2011-2012 Date and Site LOI550(%) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 3x SD p = 0.0-6.23%

33. Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01 SQuiRT AET = 18000 mg/kg 3x SD p = 4709-32289 mg/kg

34. 10000 15000 20000 25000 30000 Aluminum in Sediments from the Outer Saint John Harbour, 2011-2012 Date and Site Al(mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 SQuiRT AET = 18000 mg/kg 3x SD p = 4709-32289 mg/kg

35. 0 50000 100000 150000 200000 Iron in Sediments from the Inner Saint John Harbour, 2011-2012 Date and Site Fe(mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 02Site 03 Site 01 3x SD p = 8807-31705 mg/kg SQuiRT AET = 220000 mg/kg

36. 0 50000 100000 150000 200000 Iron in Sediments from the Outer Saint John Harbour, 2011-2012 Date and Site Fe(mg/kg dw) Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Aug 2011 Oct 2011 Jun 2012 Apr 2012 Site 06Site 13 Site 04 SQuiRT AET = 220000 mg/kg 3x SD p = 8807-31705 mg/kg

39. Triclosan Testing Cost of Method Development $4100 –Includes labour, standards and other consumables Cost/sample = $81 –Includes labour Overhead would be applied both costs –unless the funding is from a NSERC CRD grant (industry partnership)