developing a cumulative effects monitoring program for the saint john harbour – contaminants karen...
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Developing a Cumulative Effects Monitoring Program for the Saint John Harbour –
Contaminants
Karen Kidd and Angella MercerCanadian Rivers Institute, UNB Saint John
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
Concentrations of Some Metals Highly Variable in Harbour – Example is Copper
from report by Land & Sea Environmental Consultants
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?
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
Methods for Sediments – Phase IField• Surface sediment grabs at 6 reference sites• 5-10/site
– Same timing and sites as invertebratecollections– Sampled top 5 cm of sediments – Frozen until processed
Methods – Phases 1 & 2Lab 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
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)
Cont
amin
ant l
evel
s
Sites
reference level
My site
threshold effects level
What are the exposures?Some information on contamination levels so my site can be put in perspectiveSome information on thresholds and reference levels
010
020
030
040
0Zinc in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
Zn (m
g/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 SDp = 16.1-77.9 mg/kg
Aug 2011
Oct 2011
Jun 2012
Apr 2012
Aug 2011
Oct 2011
Jun 2012
Apr 2012
Site 02 Site 03Site 01
010
020
030
040
0Zinc in Sediments from the Outer Saint John Harbour, 2011-2012
Date and Site
Zn (m
g/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 06 Site 13Site 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 SDp = 16.1-77.9 mg/kg
010
2030
4050
Arsenic in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
As (m
g/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 SDp = 2.0-11.3 mg/kg
Site 02 Site 03Site 01
010
2030
4050
Arsenic in Sediments from the Outer Saint John Harbour, 2011-2012
Date and Site
As(m
g/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 06 Site 13Site 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 SDp = 2.0-11.3 mg/kg
01
210
3050
Total PAHs in Sediments from the Inner Saint John Harbour, 2011-2012TP
AHs(
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 02 Site 03Site 01Date and Site
Past Results:
Little River= 0.0-46.55 mg/kg
3x SDp = 0.0-0.59 mg/kg
noaa SQuiRT PEL=16.7 mg/kg
noaa SQuiRT Threshold=1.6 mg/kg
01
210
3050
Total PAHs in Sediments from the Outer Saint John Harbour, 2011-2012TP
AHs(
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 06 Site 13Site 04Date 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 SDp = 0.0-0.59 mg/kg
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
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)
Phase I and II - Sites for Oct 2012 Sampling
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
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)
020
4060
8010
0Copper in Sediments from the Inner Saint John Harbour, 2011-2012
Cu (m
g/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 SDp = 0.0-16.3 mg/kg
Site 02 Site 03Site 01
020
4060
8010
0Copper in Sediment from the Outer Saint John Harbour, 2011-2012
Date and Site
Cu (m
g/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 06 Site 13Site 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 SDp = 0.0-16.3 mg/kg
01
23
45
Cadmium in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
Cd (m
g/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 SDp = 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 02 Site 03Site 01
01
23
45
Cadmium from Sediments in the Outer Saint John Harbour, 2011-2012
Date and Site
Cd (m
g/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 06 Site 13Site 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 SDp = 0-0.23 mg/kg
020
4060
8010
012
0Lead in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
Pb(m
g/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 SDp = 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 02 Site 03Site 01
020
4060
8010
012
0Lead in Sediments from the Outer Saint John Harbour, 2011-2012
Date and Site
Pb(m
g/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 06 Site 13Site 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 SDp = 2.9-15.2 mg/kg
050
100
150
Chromium in Sediments in the Inner Saint John Harbour, 2011-2012
Date and Site
Cr(m
g/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 02 Site 03Site 01
3x SDp = 8.7-42.8 mg/kg
050
100
150
Chromium in Sediments for the Outer Saint John Harbour, 2011-2012
Date and Site
Cr(m
g/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 06 Site 13Site 04
CCME PEL=160 mg/kg
CCME ISQG = 30.2 mg/kg
3x SDp = 8.7-42.8 mg/kg
010
020
030
040
050
060
070
0Mercury in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
THg(
ug/k
g 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 SDp = 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 02 Site 03Site 01
010
020
030
040
050
060
070
0Mercury in Sediments from the Outer Saint John Harbour, 2011-2012
Date and Site
THg
(ug/
kg d
w)
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 06 Site 13Site 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 SDp = 0.0-24.0 ug/kg
05
1015
2025
Loss on Ignition 550 in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
LOI5
50(%
)
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 02 Site 03Site 01
3x SDp = 0.0-6.23%
05
1015
2025
Loss on Ignition 550 in Sediments from the Outer Saint John Harbour, 2011-2012
Date and Site
LOI5
50(%
)
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 06 Site 13Site 04
3x SDp = 0.0-6.23%
1000
015
000
2000
025
000
3000
0Aluminum in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
Al(m
g/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 02 Site 03Site 01
SQuiRT AET = 18000 mg/kg
3x SDp = 4709-32289 mg/kg
1000
015
000
2000
025
000
3000
0Aluminum in Sediments from the Outer Saint John Harbour, 2011-2012
Date and Site
Al(m
g/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 06 Site 13Site 04
SQuiRT AET = 18000 mg/kg
3x SDp = 4709-32289 mg/kg
050
000
1000
0015
0000
2000
00Iron in Sediments from the Inner Saint John Harbour, 2011-2012
Date and Site
Fe(m
g/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 02 Site 03Site 01
3x SDp = 8807-31705 mg/kg
SQuiRT AET = 220000 mg/kg
050
000
1000
0015
0000
2000
00Iron in Sediments from the Outer Saint John Harbour, 2011-2012
Date and Site
Fe(m
g/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 06 Site 13Site 04
SQuiRT AET = 220000 mg/kg
3x SDp = 8807-31705 mg/kg
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)