Toxicology Centre
Chemodynamic behavior of Thallium in
the Slave River, Northwest Territories,
Canada
Brett Tendler, Allison Hill, Ehimai Ohiozebau, John Giesy, and Paul Jones
ATW 2013
Toxicology Centre
Project Background
•Current open-pit mining
activities in the Alberta oil sands
are adjacent to the Athabasca
River
•Aerial emissions and oil sands
process-affected waters contain
many different chemicals
including metals PAHs, and
naphthenic acids.
•Concerns have been raised by
local communities about possible
effects of these chemicals.
Photo by Edward Burtynsky
• Concerns include human health, cultural, and economic effects.
• More information on potential environmental impacts is needed.
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Toxicology Centre
Locations
Fort Resolution (FR)
Fort Smith (FS)
Fort Chipewyan (FC)
Oil Sands Projects
Fort MacKay (FM)
Fort McMurray (FMU)
Upstream (US)
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Toxicology Centre
Sampling Procedure
Goldeye (Hiodon alosoides) GE
Walleye (Sander vitreus) WE
Whitefish (Coregonus clupeaformis) WF
•
•
•
•
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Pike or Jackfish (Esox lucius) JF
Burbot (Lota lota) BB
Fish were collected from 8 sites at 4 different time points.
Target sample size for each site was 30 individuals of species.
Each fish was subject to a standardized external and internal health assessment.
Tissue samples were collected and preserved.
Toxicology Centre
Metal Analysis Procedure
Taken from: http://www.see.uwa.edu.au/research/coralreef-marine/facilities
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• Dry muscle was added to a Teflon vial
and digested in concentrated nitric
acid (69%) and hydrogen peroxide
(30%).
• Digestates were evaporated to
dryness at 70ᴼC.
• 2% nitric acid was added to dry
sample which was then filtered and
transferred into an HDPE vial for
storage and analysis.
• Concentrations of 20 metals were
measured by ICP-MS.
Toxicology Centre
Results: Vanadium
Summer 2011
Fall 2011
150
300
100
200
SPP$
GE
JF
WE
WF
50
0
FMU
FM
FC
LOC$
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V (ug/Kg)
400
V (ug/Kg)
200
FS
FR
SPP$
GE
JF
WE
WF
100
0
FMU
FM
FC
LOC$
FS
FR
Toxicology Centre
Results: Selenium
Summer 2011
Fall 2011
8,000
6,000
7,000
5,000
Se (ug/kg)
4,000
5,000
3,000
4,000
SPP$
2,000
GE
JF
WE
WF
1,000
0
FMU
FM
FC
Location
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Se (ug/kg)
6,000
FS
FR
3,000
SPP$
2,000
GE
JF
WE
WF
1,000
0
FMU
FM
FC
Location
FS
FR
Toxicology Centre
Results: Thallium
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Toxicology Centre
Additional Sampling Sites for 2012
Fort Resolution (FR)
Fort Smith (FS)
Fort Fitzgerald (FF)
Peace Point (PP)
Fort Chipewyan (FC)
Oil Sands Projects
Fort MacKay (FM)
Fort McMurray (FMU)
Upstream (US)
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Toxicology Centre
Results 2012
Spring 2012
6,000
5,000
Se (ug/kg)
4,000
3,000
SPP$
2,000
GE
JF
WE
WF
1,000
0
FMU FM
FC
PP
FF
FS
FR
Location
300
V (ug/kg)
200
SPP$
100
0
GE
JF
WE
WF
FMU FM
FC
PP
FF
Location
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FS
FR
Toxicology Centre
Statistics
Metal
Site
BB Mean ± SE (n) *
p-value GE Mean ± SE (n)*
p-value
JF Mean ± SE (n)*
p-value
WE Mean ± SE (n)*
p-value WF Mean ±SE (n)*
p-value
Tl
FMU
8.94±0.42 (3)
0.003
0.234
14.45±2.36 (13) B
<0.001
20.94±3.61 (13) C
<0.001
<0.001
FM
0.05 (2)
9.26±1.28 (20) A
8.02±1.32 (19) B
19.96±3.10 (20) C
6.32±0.70 (20) B
FC
8.88±3.38 (4)
12.04±2.13 (19) A
16.84±2.22 (20) B
37.4±2.00 (15) B
6.85±1.26 (20) B
FS
8.43±1.36 (8) B
13.70±1.82 (20) A
32.82±4.00 (21) A
66.16±6.97 (20) A
20.30±2.70 (18) A
FR
15.99±1.53 (30) A
15.44±2.98 (12) A
47.72±5.41 (21) A
78.54±7.96 (10) A
17.59±1.19 (20) A
FMU
1848±166 (3)
FM
1476±121 (2)
2397±205 (20) B
843±118 (19) C
1432±137 (20) C
1546±78 (19) C
FC
2282±164 (4)
3262±216 (19) AB
1639±105 (20) A
2041±106 (15) AB
1509±105 (20) C
FS
1984±201 (8) A
3549±353 (20) A
1879±80 (21) A
2338±108 (20) A
2069±136 (18) AB
FR
1806±71 (30) A
4053±456 (12) A
1869±94 (21) A
2303±94 (10) AB
2233±89 (20) A
FMU
46.6±2.0 (3)
FM
20.5±2.1 (2)
20.9±3.4 (20) A
16.3±2.8 (19) A
16.8±3.6 (20) A
18.8±3.4 (20) A
FC
12.7±3.2 (4)
18.5±3.8 (19) A
23.7±5.1 (20) A
25.5±8.0 (15) A
37.0±5.6 (20) A
FS
66.3±16.4 (8) A
35.6±8.7 (20) A
25.0±5.7 (21) A
34.1±6.4 (20) A
40.7±8.4 (18) A
FR
28.8±3.6 (30) B
36.0±4.2 (12) A
14.0±4.0 (21) A
17.7±5.7 (10) A
49.2±16.5 (20) A
Se
V
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0.308
0.031
11.51±1.50 (11) A
3060±340 (11) AB
22.3±5.4 (11) A
0.005
0.141
1205±106 (13) B
22.3±4.4 (13) A
<0.001
0.208
1717±146 (13) BC
25.3±5.8 (13) A
<0.001
0.265
6.75±1.51 (10) B
1612±133 (10) BC
35.7±8.0 (10) A
<0.001
0.096
Toxicology Centre
Why Thallium is important
• Thallium is poorly understood – chemically and biologically
• Anthropogenic sources include:
•
Fossil Fuel Extraction
•
Potassium based fertilizers
• Thallium is toxic to aquatic organisms (comparable to Cu toxicity)
• Three forms of thallium occur in environment.
• Tl+
• Tl3+
• Dimethyl thallium (CH3)2Tl+
• Thallium concentrations measured in fish do not represent a risk to
human consumers based on current consumption limits
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Toxicology Centre
Questions
•
•
•
•
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Why are Tl concentrations higher in some fish species in the Slave river ?
What forms/species of Tl are accumulating in fish of the Slave river ?
Why are Tl concentrations greater in higher trophic level species ?
Does Tl originate from oil sands activities ?
Toxicology Centre
Future work
1.
2.
3.
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Analyze Livers for metals
•
ICP-MS
•
Compare to muscle concentrations
Thallium Speciation
•
Develop method HPLC/ICP-MS
Stable Isotope analysis
Toxicology Centre
Acknowledgements
Thanks to all who made contributions including:
• Garry Codling
• Eric Higley
• Dr. Karsten Liber and lab
• Erin Kelly and ENR personnel
• Tim Barrett and Kelly Munkittrick – statistical analysis
• Slave River and Delta Partnership
• Deninu School, Fort Resolution
• Aurora College, Fort Smith
• Deninu Kue First Nation, Fort Resolution Metis Council, Hamlet of Fort
Resolution, Salt River First Nation, Smith’s Landing First Nation, Town
of Fort Smith, Fort Smith Metis Council, Athabasca Chipewyan First
Nation, Mikisew Cree First Nation, Fort Mackay First Nation, Fort
McMurray First Nation, Fort McMurray Metis Council
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Toxicology Centre
Questions?
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