www.usask.ca/sens

Describe the spatial and seasonal distribution of polycyclic aromatic hydrocarbons (PAH) in bile and muscle of selected fish species www.usask.ca/sens

 PAHs originate from natural (e.g., forest fires, natural hydrocarbon seeps) and anthropogenic sources (e.g., combustion of fossil fuels & coal burning)
 Increased industrial activity in the Peace/Athabasca river basin, particularly development of the oil sands, has been a source of concern to First Nation and Metis communities
 Monitoring of fish can be used as an integrative measure of concentrations of contaminants over time and be an indicator of possible human health risks from consumption www.usask.ca/sens

www.usask.ca/sens

 Their abundance along the basin (some have short ranges, e.g., northern pike)
 Their dietary/nutritional significance to communities in the area
 Feeding strategy, such as benthic, suprabenthic, or pelagic and, trophic status, patterns of migration and habits of spawning of different fishes www.usask.ca/sens

•
•
•
Fishes were collected in the summer and fall of 2011 -2012
Length and mass recorded, photographs of whole fish and any external anomalies, fins, skin, eyes and scales examined carefully and systematically
Internal tissues preserved for analysis (biochemical and chemical) www.usask.ca/sens


5 µl sample of bile was diluted 1000 fold with 50% methanol/H
2 min at 4 0 C
O (v/v) and centrifuged at 10,000 g for 15
 Fluorescence was detected at 290/335nm for 2 and 3ring, 341/383 for 4-ring, and 380/430nm for 5-ring PAH metabolites
 Quantification was calibrated using a seven-point calibration curve of pure standards: anthracene (100-
3000 ppb), chrysene (100-5000 ppb) and benzo(a)pyrene
(0.1-50 ppb) measured simultaneously with the samples www.usask.ca/sens

Burbot
Goldeye 22
Jackfish 30
Walleye 20
Fort
Resolution
26 9
Fort
Smith
30
30
30
Whitefish 30
Total 128
23
122
30
30
25
Fort
Chipewyan
5 2
Fort
McKay
30
120
30
24
30
22
108
21
23
23
6
Fort
McMurray
14
87
48
133
137
128
119
565
Total www.usask.ca/sens

Significant differences were observed among sites for 2 and 3-ring PAH metabolites
(F
5.88
=3.15; p =
0.0004) and for 5-ring type PAH metabolites
(F
6.42
= 3.15, p =
0.0002)
9000.0
8000.0
7000.0
6000.0
5000.0
4000.0
3000.0
2000.0
1000.0
0.0
Fort
McMurray
Fort McKay Fort
Chipewyan
Fort Smith Fort
Resolution
Burbot
Goldeye
Jackfish
Walleye
Whitefish www.usask.ca/sens

www.usask.ca/sens

• The mean of the three seasons was greatest in
Fort McKay, followed by Fort McMurray
• The range of data was great especially those of Fort McMurray,
Fort McKay and Fort
Chipewyan www.usask.ca/sens

 Spatial and seasonal peaks coincided with fishes in locations proximate to oil sands operations
 Trophic level and habitat preference of selected fishes were important factors in accounting for the concentrations of PAH in bile of fishes
 Results will be valuable for establishing the status of trends and spatial distribution of PAHs during monitoring of the lower Peace/Athabasca/Slave basin www.usask.ca/sens

Burbot
Fort
Resolution
Fort Smith Fort Fort
Chipewyan McKay
22 8 5 2
18 16 28 Goldeye 12
Jackfish 24 19 20 20
23 15 23 Walleye 17
Whitefish 26
Total 101
18
86
18
74
20
93
18
11
71
Fort
McMurray
6
15
21
Total
43
89
104
96
93
425 www.usask.ca/sens

70
56
42
28
14
0
Significant differences were observed among sites for all species combined www.usask.ca/sens

Distribution of Parent PAHs in the Sampled Locations
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
Fort McMurray Fort McKay Fort Chipewyan
2-ring 3-ring 4-ring 5-ring 6-ring
Fort Smith Fort Resolution www.usask.ca/sens

 Measurable concentrations of PAHs were detected across spatial and seasonal studies
 2-3-ring PAHs were predominant, and 4-ring PAHs were abundant
 The concentration of the muscle total PAHs was highest in whitefish
 Fishes from the upstream portions of the Athabasca
River, which were nearer to locations where oil sands are extracted and upgraded, contained greater concentrations of individual PAHs than fishes from the
Slave River www.usask.ca/sens

Results: PAH (BaP Equivalent)Toxicity Across
Locations
14
12
10
Burbot
Goldeye
Jackish
Walleye
Whitefish
8
6
4
2
0
Fort McMurray Fort McKay Fort Chipewyan Fort Smith Fort Resolution
The concentrations of TEBaP eq their sampling locations.
(ngg -1 wm) values of different fish species, in respective to www.usask.ca/sens

0.0006
0.0009
0.0008
0.0009
0.002
Fort McMurray
Fort McKay
Fort Chipewyan
Fort Smith
Fort Resolution
 A person of 70 kg body weight consumes an estimated 227 g of fish per day (USEPA 1991a). www.usask.ca/sens

From these results, it is unlikely that PAH derived from consumption of fishes derived in the Athabasca and Slave Rivers watershed represent a significant human health concern www.usask.ca/sens

• Alkylated PAH concentration ranged from the detection limit to 134 ng/g wm
• The greatest concentration of naphthalene is seen at N
2
(13 ng/g, wm)
• Fluorene had the greatest concentration at F
2
(4.9 ng/g, wm)
• A bell shape distribution of parent PAHs and their alkylated analogous is likely represent a petrogenic source
• The distribution of the 2- and 3- ring
PAHs were generally bell shaped www.usask.ca/sens

RESULTS: Contd.
• The presence of naphthalene in environmental samples is generally associated with un-weathered petroleum
(Headley et al. 2002)
• The prevalence of naphthalene in the sampled locations is likely that they are from sediments and biota impacted by relatively fresh petroleum sources www.usask.ca/sens



Naphthalene was the most prevalent compound, contributing the highest concentration to the total PAH budget, characteristic of PAH mixture generated by petrogenic pollution (Pampanin and Sydnes 2013)
The pattern of alkylation from the different locations does not appear to be different. However, subtle differences exist that require further studies
 The PAH concentrations rapidly decline downstream to values typical of remote pristine areas (Headley et al. 2001)
 The PAHs are derived predominantly from petrogenic sources, likely a combination of natural oil sands deposits and development www.usask.ca/sens

•
•
The greatest concentration of PAHs were observed in the vicinity of Fort McKay and Fort McMurray
The distribution of PAHs and their alkylated analogues shows low molecular weight PAHs as the most prevalent compounds, indicative of PAH mixtures generated by petrogenic pollution www.usask.ca/sens










My supervisor, Dr. Paul Jones
Brett Tendler, Allison Hill, Tim Tse, Jon Doering, Eric Higley,
Garry Codling,
Prof John Giesy
Erin Kelly, Jen Fresque-Baxter (ENR GNWT)
ENR Ft. Smith
Slave River and Delta Partnership
Boreal Songbird Initiative, AANDC, GNWT – Funding
CWN for funding – 2013-2014 sampling
Ft. Resolution Metis Council, Deninu Kue First Nation, Deninu
School, Ft. Smith Metis Council, Smith’s Landing First Nation,
Hamlet of Ft. Resolution, Town of Ft. Smith, Salt River First
Nation, NWT Metis Council, Parks Canada www.usask.ca/sens