Per- and Polyfluoroalkyl Substances in the Duluth, Minnesota Area: Exposure to and Biomarker Responses in Tree Swallows Relative to Known Fire-Fighting Foam Sources
<p>Map of per- and polyfluorinated substances (PFAS) study sites in the Duluth, MN area 2019–2021. Two underlined site names are known as locations at which aqueous film forming foams (AFFFs) were used. Note: ANG = Duluth Air National Guard Base and UMD = farm at University of Minnesota, Duluth.</p> "> Figure 2
<p>Correlation between original 13 (PFAS<sub>13</sub>) and current 40 (PFAS<sub>40</sub>) per- and polyfluoroalkyl substances (PFAS) in tree swallow eggs from the Duluth, MN area in 2021. Lower panel is an enlargement of the lower end of the distribution.</p> "> Figure 3
<p>Total mass (ng) of perfluorooctane sulfonate (PFOS) in pairs of eggs and sibling 12- to 15-day old nestlings at Rice Lake North and the reference site (Boulder Lake, upper panel) in the Duluth, MN area in 2020–2021. Lower panel is expanded to provide more detail at the reference lake. Average accumulation rates (ng/day) are provided for the two sites.</p> "> Figure 4
<p>Correlation between the sum of 40 per- and polyfluoroalkyl substances (PFAS<sub>40</sub>) in diet and nestling carcasses (<b>upper</b>) and diet and eggs (<b>lower</b>) from the Duluth, MN area in 2020–2021.</p> "> Figure 5
<p>Nonmetric multidimensional scaling (NMDS) plot of per- and polyfluoroalkyl substances (PFAS) in tree swallow nestlings (2010 and 2021) by region in the Duluth, MN area for n = 25 PFAS detected in ≥2 samples. Note: NMDS plots are unitless, AFFF = aqueous film forming foam, SLR = St. Louis River.</p> "> Figure 6
<p>Nonmetric multidimensional scaling (NMDS) plot of per- and polyfluoroalkyl substances (PFAS) in tree swallow egg, nestling, and diet samples (2010 and 2021) in the Duluth, MN area for n = 27 PFAS detected in ≥2 samples in at least one of the three matrices. Note that NMDS plots are unitless.</p> "> Figure 7
<p>Average percentage of 40 per- and polyfluoroalkyl substances (PFAS<sub>40</sub>) that individual PFAS comprised in tree swallow nestling carcasses in the three regions near Duluth, MN 2020–2021. St. Louis River includes Boy Scout Landing which has an aqueous film forming foam (AFFF) source and has been pulled out for visualization. Percentages inside circles are for perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS). Concentrations or range of total PFAS<sub>40</sub> concentrations are provided for sites within each region in parentheses. Note: AFFF = aqueous film forming foam, PFOA = perfluorooctanoate, PFNA = perfluorononanoate, PFDA = perfluorodecanoate, PFUnA = perfluoroundecanoate, PFDoA = perfluorododecanoate, PFTrDA = perfluorotridecanoate.</p> "> Figure 8
<p>Average percentage of 40 per- and polyfluoroalkyl substances (PFAS<sub>40</sub>) that individual PFAS comprised in tree swallow eggs in the three regions near Duluth, MN 2020–2021. St. Louis River includes Boy Scout Landing, which has been pulled out (lower right) for visualization. Percentages inside circles are for perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS). Concentrations or range of total PFAS<sub>40</sub> concentrations are provided for sites within each region in parentheses. Note: AFFF = aqueous film forming foam, PFOA = perfluorooctanoate, PFNA = perfluorononanoate, PFDA = perfluorodecanoate, PFUnA = perfluoroundecanoate, PFDoA = perfluorododecanoate, PFTrDA = perfluorotridecanoate.</p> "> Figure 9
<p>Ratio of total carboxylates to total sulfonates in tree swallow eggs (<b>upper</b>) and in nestlings (<b>lower</b>) at sites in the three regions near Duluth, MN, 2020–2021.</p> ">
Abstract
:1. Introduction
2. Materials and Methods
2.1. Chemical Analyses
2.2. Biomarker Assessments
2.3. Statistical Analyses
3. Results
3.1. PFAS Exposure
- (1)
- PFAS40Estimate = 1.216 × PFAS13 + 24.48 for eggs
- (2)
- PFAS40Estimate = 1.039 × PFAS13 + 7.005 for nestlings
- (3)
- PFAS13Estimate = 0.820 × PFAS40 − 19.017 for eggs
- (4)
- PFAS13Estimate = 0.876 × PFAS40 − 2.433 for nestlings
3.2. PFAS Composition—Regional and Site Comparisons
3.3. Contribution of Individual PFAS to Total PFAS
3.4. Carboxylic Acid to Sulfonate Ratios
3.5. Organochlorine and Trace Element Contaminants
3.6. Biomarkers
4. Discussion
4.1. PFAS Exposure
4.2. Other Chemical Exposures
4.3. Biomarker Responses
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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PFAS and Sample Size | Eggs | Nestling | Diet |
---|---|---|---|
Sample size (n) | 47 | 83 | 9 |
Sulfonates | |||
PFOS | 100 | 99 | 100 |
PFHxS | 96 | 86 | 67 |
PFDS | 91 | 60 1 | 22 |
Carboxylic acids | |||
PFOA | 72 | 90 | 89 |
PFNA | 100 | 99 | 100 |
PFDA | 98 | 88 | 33 |
PFUnA | 98 | 71 | 33 |
PFDoA | 100 | 52 | 0 |
PFTrDA | 87 | 19 1 | 0 |
PFTeDA | 79 | 19 1 | 0 |
Other types | |||
N-EtFOSE | 64 | 20 1 | 0 |
7:3 FTCA | 60 | 23 1 | 11 |
6:2 FTS | 13 | 17 1 | 56 |
EtFOSAA | 6 | 56 1 | 11 |
St. Louis River | North Region | Reference | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
PFAS | Thomson Reservoir | Boy Scout Landing | Munger Landing | Erie Ponds | Miller Creek | ANG | Martin Road | Rice Lake North | UMD | Boulder Lake |
n = 9 | n = 6 | n = 6 | n = 3 | n = 5 | n = 4 | n = 3 | n = 3 | n = 2 | n = 5 | |
Sulfonates | ||||||||||
PFOS | 10.49 C 1 (7.60–14.48) 5.60–17.50 | 34.80 BC (14.49–83.57) 18.32–107 | 16.31 BC (11.45–23.24) 9.91–27.3 | 18.25 BC (14.50–22.97) 16.50–19.80 | 6.52 C (4.32–9.85) 4.38–8.67 | 136.90 AB (25.20–743) 29.50–339 | 92.08 AB (58.27–145.52) 81–114 | 469.7 A (28.25–7809) 181–1640 | 26.64 BC (8.29–85.57) 24.30–29.20 | 6.08 C (4.22–8.74) 3.93–8.24 |
PFHxS | 0.23 CD (0.17–0.31) 0.13–0.39 | 1.52 BC (0.78–2.96) 0.73–3.55 | 0.39 CD (0.28–0.54) 0.26–0.61 | 0.50 CD (0.36–0.68) 0.44–0.56 | 0.26 CD (0.17–0.41) 0.15–0.39 | 11.00 AB (1.64–74.00) 2.60–42.8 | 4.47 AB (1.11–17.96) 2.95–8.45 | 31.74 A (0.85–1192) 12.90–171 | 1.14 BC (0.17–7.55) 0.98–1.32 | 0.12 D (0.07–0.21) 2ND-0.19 |
Carboxylic acids | ||||||||||
PFOA | 0.25 BCD (0.12–0.53) 3ND 2-0.91 | 0.28 BCD (0.14–0.58) 1ND-0.55 | 0.17 CD (0.08–0.34) 3ND-0.43 | 0.12 CD (0.05–0.29) 2ND-0.18 | 0.10 D (0.08–0.13) 4ND-0.14 | 1.24 B (0.17–9.12) 0.20–3.06 | 0.44 BCD (0.15–1.31) 0.29–0.69 | 11.70 A (0.12–1142) 3.62–98.0 | 1.11 ABC (0.04–30.65) 0.85–1.44 | 0.37 BCD (0.21–0.66) 0.23–0.81 |
PFNA | 1.50 BC (0.93–2.43) 0.71–4.26 | 1.40 BC (0.58–3.35) 0.58–6.28 | 1.03 BC (0.79–1.34) 0.77–1.59 | 0.51 C (0.37–0.7) 0.44–0.57 | 0.60 C (0.29–1.21) 0.29–1.39 | 2.63 AB (0.45–15.16) 0.51–5.29 | 0.82 BC (0.46–1.46) 0.63–0.97 | 11.03 A (0.33–363) 3.71–54.0 | 1.47 BC (0.23–9.37) 1.27–1.70 | 1.02 BC (0.72–1.44) 0.74–1.45 |
PFDA | 0.81 A (0.56–1.18) 0.44–1.99 | 0.96 A (0.38–2.47) 0.37–5.18 | 0.96 A (0.47–1.94) 0.55–3.38 | 0.63 A (0.33–1.21) 0.47–0.74 | 0.62 A (0.45–0.86) 0.48–0.96 | 1.27 A (0.06–2)8.10 1ND-6.14 | 0.68 A (0.61–0.76) 0.66–0.72 | 2.39 A (0.14–41.4) 0.90–8.44 | 0.73 A (0.04–12.71) 0.58–0.91 | 0.64 A (0.44–0.93) 0.46–0.89 |
PFUnA | 1.29 A (0.99–1.68) 0.76–2.31 | 1.51 A (0.59–3.87) 0.54–7.61 | 1.05 A (0.81–1.36) 0.80–1.59 | 0.68 A (0.43–1.07) 0.55–0.79 | 0.62 A (0.42–0.90) 0.42–0.80 | 1.12 A (0.06–20.50) 1 ND-3.49 | 0.98 A (0.93–1.05) 0.96–1.0 | 2.03 A (0.15–28.2) 0.77–6.28 | 0.89 A (0.59–1.34) 0.86–0.92 | 1.35 A (0.84–2.18) 0.91–2.2 |
PFDoA | 0.61 AB 3 (0.46–0.81) 0.35–1.4 | 0.86 AB (0.30–2.47) 0.31–4.56 | 0.60 AB (0.46–0.78) 0.43–0.82 | 0.70 AB (0.44–1.12) 0.57–0.80 | 0.65 AB (0.36–1.18) 0.45–1.50 | 1.63 A (0.34–7.79) 0.49–5.48 | 0.65 AB (0.50–0.83) 0.61–0.73 | 0.88 AB (0.05–15.32) 0.34–3.17 | 0.71 AB (0.003–147.9) 0.47–1.08 | 0.51 B (0.30–0.88) 0.32–0.88 |
PFTrDA | 0.47 A (0.20–1.06) 2ND-1.33 | 1.13 A (0.49–2.61) 0.44–4.33 | 0.33 A (0.10–1.14) 2ND-0.81 | 0.33 A (0.01–8.15) 1ND-0.70 | 0.63 A (0.40–1.01) 0.42–1.08 | 1.23 A (0.34–2.86) 0.60–1.71 | 0.75 A (0.58–0.99) 0.67–0.81 | 0.64 A (0.004–108.9) 1ND-4.49 | 0.82 A (0.02–31.4) 0.61–1.09 | 0.74 A (0.36–1.54) 0.37–1.33 |
PFTeDA | 0.27 A (0.17–0.42) 1ND-0.58 | 0.29 A (0.09–0.94) 2ND-1.09 | 0.24 A (0.09–0.62) 2ND-0.63 | 0.37 A (0.17–0.84) 0.26–0.45 | 0.21 A (0.17–0.25) 0.17–0.25 | 0.61 A (0.07–5.62) 1ND-1.45 | 0.14 A (0.01–1.92) 2ND-0.48 | 0.35 A (0.005–27.24) 1ND-2.4 | 0.25 A (0.00001–519,704) 1ND-0.77 | 0.31 A (0.22–0.44) 0.25–0.43 |
Others | ||||||||||
PFDS | 0.40 AB 4 (0.29–0.55) 0.23–0.98 | 0.47 AB (0.20–1.06) 0.18–1.87 | 0.36 AB (0.25–0.52) 0.26–0.68 | 1.57 A (0.55–4.49) 1.00–2.30 | 0.26 AB (0.15–0.46) 0.18–0.54 | 0.57 AB (0.04–9.01) 1ND-5.01 | 0.16 B (0.10–0.25) 0.13–0.18 | 0.19 AB (0.003–10.41) 2ND-1.21 | 0.28 AB (0.01–7.53) 0.22–0.37 | 0.20 AB (0.09–0.43) 1ND-0.40 |
N-EtFOSE | 1.23 A (0.73–2.06) 2ND-3.32 | 2.22 A (0.55–8.96) 2ND-14 | 1.47 A (0.47–4.59) 3ND-7.27 | 0.71 A (0.30–1.65) 2ND-1.05 | 0.72 A (0.49–1.06) 3ND-1.11 | 1.75 A (0.22–13.70) 3ND-7.04 | 2.13 A (1.09–4.15) 1.5–2.66 | 2.19 A (0.03–147.7) 1ND-14.80 | 1.07 A (0.001–2383) 1ND-1.96 | 1.24 A (0.77–1.99) 0.85–2.07 |
7:3 FTCA | 4.10 AB 5 (1.26–13.31) 5NA 6; 1ND-10.2 | 15.04 AB (7.73–29.26) 2NA; 10.82–27.6 | 4.04 B (0.70–23.29) 3NA; 1ND-8.32 | 19.95 AB (4.72–84.35) 11.80–37.20 | 7.57 AB (5.74–9.98) 5.62–10.10 | 25.32 AB (3.26–197) 7.27–154 | 8.78 AB (4.27–18.06) 1NA; 8.30–9.30 | 35.89 AB (0.00001–95,716,627) 1NA; 11.2–115 | 8.12 AB (5.28–12.49) 7.85–8.40 | NA |
Total PFAS13 | 15.51 BC (11.36–21.17) 8.71–24.97 | 42.46 BC (18.27–98.71) 21.07–134 | 20.58 BC (14.42–29.38) 12.87–35.68 | 21.36 BC (17.11–26.66) 19.34–23.00 | 9.51 C (6.77–13.36) 6.63–11.88 | 157.4 AB (28.20–879) 33.29–20.55 | 100.4 AB (61.21–164.64) 87.65–126 | 534.7 A (28.85–9909) 204–1981 | 32.74 BC (8.03–133.5) 29.31–36.57 | 10.13 C (6.85–14.97) 6.62–13.54 |
Total PFAS40 | 19.84 C (14.36–27.42) 10.8–32.62 | 57.97 BC (26.0–129.25) 24.39–183 | 27.57 C (17.63–43.11) 20.52–64.62 | 45.43 BC (20.79–99.28) 33.82–63.27 | 38.19 C (8.03–181.62) 17.51–355 | 208.2 AB (41.93–1034) 53.07–598 | 109.9 AB (65.46–184.56) 95.98–140 | 600.6 A (22.03–16,373) 206–2665 | 43.52 C (10.31–183.67) 38.86–48.74 | 13.71 C (8.83–21.26) 8.24–19.23 |
Percentage 13 of 40 | 78.2 | 73.2 | 74.6 | 47.0 | 24.9 | 75.6 | 91.3 | 89.0 | 75.2 | 73.9 |
PFAS | St. Louis River | North Region | Reference | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Thomson Reservoir | Boy Scout Landing | Munger Landing | Stryker Bay | Erie Ponds | Miller Creek | ANG | Martin Road | Rice Lake North | UMD | Boulder Lake | |
n = 14 | n = 6 | n = 17 | n = 5 | n =14 | n = 5 | n = 5 | n = 5 | n = 6 | n = 1 | n = 5 | |
Sulfonates | |||||||||||
PFOS | 8.86 CD 1 (6.90–11.37) 3.29–14.30 | 12.76 BC (9.00–18.08) 8.52–18.60 | 11.63 BCD (9.97–13.56) 7.05–17.80 | 7.63 CD (5.53–10.53) 5.98–11.20 | 11.42 BCD (9.88–13.20) 8.44–19.20 | 6.08 CD (4.05–9.12) 4.08–9.80 | 36.73 AB (15.71–85.90) 17.6–109 | 82.10 A (44.89–150.1) 47.40–151 | 121.9 A (103.7–143.4) 104–155 | 3.72 D (.-.) 3.72 | 1.06 E (0.14–8.21) 1ND-2.53 |
PFHxS | 0.28 CD (0.19–0.40) 5ND 2-0.49 | 1.29 B (0.74–2.25) 0.69–2.97 | 0.55 BC (0.44–0.69) 5ND-1.01 | 5ND | 0.39 CD (0.29–0.53) 5ND-0.66 | 0.26 CD (0.20–0.33) 0.19–0.32 | 5.48 A (1.64–18.24) 1.54–21.6 | 7.00 A (5.10–9.61) 5.01–9.70 | 8.24 A (7.08–9.58) 6.93–10.5 | 0.24 CD (.-.) 0.24 | 0.17 D (0.07–0.42) 1ND-0.32 |
Carboxylic acids | |||||||||||
PFOA | 1.08 ABC (0.79–1.48) 0.38–3.37 | 0.30 CDE (0.24–0.37) 0.23–0.41 | 0.59 BC (0.48–0.72) 0.26–1.04 | 0.48 BCD (0.25–0.93) 1ND-0.75 | 0.31 CDE (0.21–0.46) 3ND-0.71 | 0.09 E (0.02–0.37) 4ND-0.68 | 1.18 AB (0.41–3.40) 0.41–3.11 | 3.81 A (1.96–7.39) 2.00–6.40 | 3.88 A (3.06–4.91) 2.95–5.59 | 0.13 DE (.-.) 0.13 | 0.76 BC (0.54–1.06) 0.49–0.97 |
PFNA | 2.05 A (1.66–2.52) 1.05–3.79 | 0.91 ABC (0.65–1.28) 0.63–1.47 | 1.12 AB (1.02–1.24) 0.79–1.69 | 0.85 ABC (0.59–1.22) 0.60–1.23 | 0.94 ABC (0.70–1.27) 0.42–2.80 | 0.44 C (0.19–0.98) 0.25–1.28 | 0.69 BC (0.46–1.05) 0.49–1.19 | 1.02 ABC (0.54–1.94) 0.64–2.03 | 1.73 A (1.28–2.32) 1.27–2.81 | 0.05 D (.-.) 1 ND | 1.40 AB (1.10–1.78) 1.10–1.68 |
PFDA | 0.53 AB (0.46–0.62) 0.32–0.75 | 0.33 AB (0.28–0.38) 0.25–0.38 | 0.42 AB (0.34–0.51) 3ND-0.67 | 0.23 B (0.15–0.36) 4ND-0.43 | 0.44 AB (0.34–0.56) 2ND-0.90 | 0.67 A (0.26–1.68) 0.31–2.15 | 0.33 AB (0.16–0.67) 0.21–0.91 | 0.39 AB (0.25–0.62) 0.25–0.62 | 0.76 A (0.59–0.98) 0.54–1.13 | 0.05 C (.-.) 1ND | 0.34 AB (0.28–0.42) 0.29–0.40 |
PFUnA | 0.57 A (0.47–0.71) 0.31–0.88 | 0.22 AB (0.10–0.47) 1ND-0.36 | 0.43 A (0.38–0.49) 1ND-0.70 | 0.31 AB (0.18–0.51) 2ND-0.45 | 0.30 AB (0.21–0.43) 4ND-0.59 | 0.08 BC (0.03–0.25) 4ND-0.42 | 0.08 BC (0.02–0.31) 4ND-0.55 | 0.05 C (.-.) 5ND | 0.24 AB (0.07–0.83) 2ND-0.72 | 0.05 C (.-.) 1ND | 0.42 A (0.34–0.53) 0.33–0.50 |
PFDoA | 0.11 ABC (0.07–0.18) 8ND-0.21 | 0.08 BC (0.05–0.11) 3ND-0.13 | 0.16 ABC (0.15–0.18) 5ND-0.21 | 5ND | 0.27 A (0.22–0.32) 5ND-0.48 | 0.17 AB (0.07–0.41) 1ND-0.36 | 0.12 ABC (0.03–0.44) 2ND-0.67 | 0.05 C (.-.) 5ND | 0.06 BC (0.04–0.09) 5ND-0.13 | 0.05 C (.-.) 1ND | 0.11 ABC (0.06–0.18) 1ND-0.15 |
Other types | |||||||||||
PFDS | 0.17 B (0.10–0.29) 5NA; 2ND-0.38 | 0.09 BC (0.06–0.14) 2ND-0.13 | 0.18 B (0.16–0.19) 5NA; 0.13–0.21 | NA | 0.57 A (0.46–0.71) 5NA; 0.33–0.88 | 0.22 AB (0.14–0.35) 0.17–0.43 | 0.09 BC (0.02–0.33) 4ND-0.60 | 0.05 C (.-.) 5ND | 0.05 C (.-.) 6ND | 0.05 C (.-.) 1ND | 0.05 C (.-.) 5ND |
N-EtFOSAA | 0.10 BC (0.05–0.18) 5NA 3; 5ND-0.48 | 0.18 B (0.13–0.26) 0.11–0.29 | 0.25 B (0.20–0.32) 5NA; 0.13–0.45 | NA | 1.08 A (0.89–1.31) 5NA; 0.75–1.63 | 0.23 B (0.08–0.67) 1ND-0.50 | 0.05 C (.-.) 5ND | 0.05 C (.-.) 5ND | 0.05 C (.-.) 6ND | 0.05 C (.-.) 1ND | 0.05 C (.-.) 5ND |
Total PFAS13 | 13.57 C (10.81–17.04) 5.50–23.49 | 16.15 C (11.59–22.51) 10.8–23.6 | 15.06 C (13.07–17.35) 9.69–22.11 | 9.40 CD (6.62–13.34) 6.87–14.03 | 14.63 C (12.66–16.91) 10.01–25.87 | 8.06 CDE (5.06–12.84) 5.66–15.01 | 45.24 B (18.75–109.1) 20.65–139.4 | 94.82 AB (52.86–170.1) 55.29–169 | 138.23 A (117.5–162.6) 116–177 | 4.09 E (.-.) 4.09 | 5.04 DE (3.80–6.69) 3.66–6.49 |
Total PFAS40 | 14.26 DE (11.53–17.65) 5.50–23.49 | 16.53 DE (11.80–23.14) 10.97–24.27 | 17.35 DE (15.23–19.77) 12.38–32.10 | 9.40 EF (6.62–13.34) 6.87–14.03 | 20.57 DE (16.80–25.17) 10.01–39.74 | 30.88 CD (25.24–37.79) 25.72–39.65 | 54.64 BC (17.35–172.1) 20.82–249.7 | 96.37 AB (54.66–169.9) 58.49–170 | 139.5 A (118.9–163.8) 117–178 | 4.09 F (.-.) 4.09 | 5.58 F (4.24–7.35) 3.88–6.81 |
Percentage 13 is of 40 | 95.1 | 97.7 | 86.8 | 100 | 71.1 | 26.1 | 82.8 | 98.4 | 99.1 | 100 | 90.3 |
Site | PFHxS | PFOS | |
---|---|---|---|
n | ng/d | ng/d | |
Reference | |||
Boulder Lake | 5 | 0.34 CD 1 | 2.70 D |
North region | |||
Rice Lake North | 6 | 8.25 A | 134.80 A |
Martin Road | 5 | 11.66 A | 130.98 A |
ANG | 5 | 7.27 A | 39.53 B |
UMD Farm | 1 | 0.16 D | 1.19 D |
St. Louis River | |||
Thomson Reservoir | 9 | 0.43 CD | 11.72 C |
Boy Scout Landing | 5 | 1.72 B | 14.35 BC |
Munger Landing | 12 | 0.89 BC | 17.16 BC |
Erie Ponds | 9 | 0.54 BC | 14.42 BC |
Miller Creek | 5 | 0.38 CD | 8.99 C |
PFAS | St. Louis River | North Region | Reference | |||||
---|---|---|---|---|---|---|---|---|
Thomson Reservoir | Boy Scout Landing | Erie Ponds | Miller Creek | ANG | Martin Road | Rice Lake North | Boulder Lake | |
Sulfonates | ||||||||
PFOS | 15.5 | 5.10 | 4.86 | 2.92 | 29.0 | 44.7 | 90.0 | 2.95 |
PFHxS | 0.29 | 0.31 | .1 | . | 3.01 | 0.54 | 1.73 | . |
Carboxylic acids | ||||||||
PFOA | 0.86 | 0.12 | 0.7 | 0.22 | 0.94 | 1.13 | 1.50 | 0.451 |
PFNA | 2.84 | 0.39 | 0.46 | 0.25 | 0.37 | 0.68 | 1.33 | 1.51 |
PFDA | 0.61 | . | . | . | . | . | 0.47 | 0.322 |
PFUnA | 0.55 | . | . | . | . | . | 0.27 | 0.283 |
6:2 FTS | . | 2.24 | 1.91 | 1.74 | . | 43.9 | 1.02 | . |
8:2 FTS | . | . | 152 | . | 0.65 | 1.03 | 0.72 | . |
Total PFAS13 | 20.6 | 5.92 | 6.02 | 3.32 | 33.3 | 47.0 | 95.30 | 5.52 |
Total PFAS40 | 20.6 | 8.15 | 160 | 5.13 | 34.0 | 92.0 | 97.0 | 5.52 |
Percentage 13 is of 40 | 100 | 72.6 | 3.8 | 66.1 | 98.1 | 51.1 | 98.2 | 100 |
Site and Year | N | Thiol | PBSH | Total GSH | Reduced GSH | GSSG | GSSG_GSH | TBARS Protein | TBARS Tissue |
---|---|---|---|---|---|---|---|---|---|
Reference | |||||||||
Boulder Lake 2021 | 6 | 38.17 AB 1 (27.43–48.91) 25.5–51.2 | 28.35 ABC (20.14–36.56) 18.3–38.2 | 16.56 AB (13.57–19.55) 13.5–20.2 | 9.82 AB 2 (7.13–12.50) 7.2–13.0 | 3.37 A (3.18–3.56) 3.2–3.6 | 0.36 A (0.28–0.44) 0.27–0.44 | 550.88 AB (229.84–871.92) 169.0–936.5 | 64.1 AB (26.28–101.95) 20.0–118.1 |
North region | |||||||||
Rice Lake North 2021 | 5 | 39.70 AB (29.94–49.46) 29.6–46.8 | 28.88 ABC (20.89–36.87) 21.8–36.6 | 17.81 A (15.37–20.25) 14.6–19.7 | 10.82 A (8.11–13.53) 7.8–13.3 | 3.49 A (2.99–4.00) 3.1–4.2 | 0.34 A (0.23–0.45) 0.24–0.44 | 327.52 AB (231.11–423.93) 246.6–436.7 | 43.68 AB (28.30–59.06) 28.2–60.9 |
Martin Road 2021 | 4 | 31.85 AB (20.34–43.36) 24.8–40.5 | 23.28 ABC (13.61–32.94) 17.5–29.2 | 15.06 AB (10.55–19.56) 12.1–18.6 | 8.59 AB (5.55–11.62) 7.3–11.3 | 3.24 A (2.30–4.17) 2.4–3.7 | 0.38 A (0.28–0.48) 0.32–0.44 | 428.1 AB (220.04–636.16) 289.0–603.3 | 49.38 AB (23.64–75.11) 30.0–69.2 |
ANG 2021 | 5 | 31.24 AB (26.19–36.29) 25.3–35.4 | 22.52 ABC (20.22–24.82) 19.8–24.9 | 14.44 AB (10.43–18.44) 10.9–18.0 | 8.75 AB (5.87–11.62) 5.6–10.9 | 2.85 A (2.07–3.63) 2.2–3.6 | 0.34 A (0.23–0.44) 0.23–0.47 | 318.76 AB (151.54–485.98) 177.2–485.5 | 32.52 AB (10.95–54.09) 15.0–59.0 |
UMD Farm 2021 | 1 | 24.00 B | 18.7 C | 9.57 B | 5.27 B | 2.15 A | 0.41 A | 115.4 B | 11.30 B |
St. Louis River | |||||||||
Thomson Reservoir 2019 | 10 | 45.35 AB (36.17–54.53) 25.6–66.1 | 36.61 ABC (28.94–44.28) 21.6–57.6 | 14.77 AB (11.66–17.88) 6.7–22.3 | 8.76 AB (6.66–10.86) 4.00–14.3 | 3.02 A (2.42–3.62) 1.40–4.00 | 0.36 A (0.31–0.41) 0.26–0.46 | 707.94 AB (499.09–916.79) 431.2–1308.4 | 84.67 AB (57.66–111.68) 53.50–173.1 |
Thomson Reservoir 2021 | 10 | 30.23 AB (22.22–38.24) 15.8–53.7 | 22.09 ABC (15.81–28.37) 12.4–41.0 | 14.56 AB (11.57–17.54) 8.3–22.4 | 8.14 AB (6.16–10.12) 3.4–12.6 | 3.21 A (2.65–3.77) 2.2–4.9 | 0.42 A (0.33–0.51) 0.31–0.74 | 830.66 A (597.76–1063.6) 304.7–1357 | 92.00 A (68.14–115.86) 33.8–157.2 |
Boy Scout Landing 2021 | 4 | 28.20 AB (6.72–49.68) 17.8–48.0 | 20.63 BC (2.66–38.59) 13.8–37.4 | 13.80 AB (6.60–21.01) 7.5–17.8 | 7.60 AB (3.29–11.91) 4.1–10.6 | 3.10 A (1.55–4.66) 1.7–3.9 | 0.415 A (0.33–0.50) 0.34–0.47 | 276.7 AB (131.59–421.81) 190.3–375.0 | 32.23 AB (14.81–49.64) 22.6–46.9 |
Munger Landing 2019 | 5 | 44.86 AB (27.20–62.52) 24.7–64.4 | 36.14 ABC (21.56–50.72) 20.5–53.2 | 14.52 AB (9.74–19.30) 8.4–19.0 | 8.72 AB (5.40–12.04) 4.2–11.2 | 2.88 A (2.06–3.70) 2.1–3.9 | 0.348 A (0.24–0.45) 0.28–0.49 | 575.42 AB (362.21–788.63) 416.7–856.6 | 59.38 AB (42.42–76.34) 41.7–76.3 |
Munger Landing 2021 | 7 | 29.27 AB (20.31–38.23) 18.3–46.8 | 21.31 ABC (13.91–28.72) 11.0–34.9 | 14.6 AB (11.18–18.02) 9.92–20.36 | 7.95 AB (5.63–10.26) 4.36–11.94 | 3.32 A (2.68–3.96) 2.11–4.21 | 0.44 A (0.34–0.54) 0.35–0.64 | 634.49 AB (464.50–804.47) 267.5–840.4 | 70.76 AB (47.66–93.86) 33.3–113.8 |
Stryker Bay 2019 | 10 | 47.85 AB (41.03–54.67) 35.2–65.6 | 38.12 AB (32.46–43.78) 28.4–52.9 | 16.90 AB (14.46–19.34) 10.9–21.1 | 9.73 AB (8.34–11.12) 6.8–12.7 | 3.58 A (2.88–4.28) 2.0–4.8 | 0.3 A (0.31–0.43) 0.28–0.53 | 477.24 AB (294.52–659.96) 204.4–988.8 | 58.29 AB (35.59–80.99) 23.1–125.9 |
Erie Ponds 2019 | 9 | 50.28 A (43.27–57.28) 37.8–62.7 | 40.544 A (34.84–46.25) 30.7–51.1 | 17.17 AB (15.14–19.19) 13.4–19.8 | 9.73 AB (8.27–11.20) 7.1–12.0 | 3.70 A (3.20–4.20) 2.6–4.5 | 0.39 A (0.33–0.45) 0.29–0.49 | 653.21 AB (571.09–735.33) 477.1–871.6 | 73.97 AB (60.87–87.06) 48.4–112.0 |
Erie Ponds 2021 | 10 | 36.74 AB (30.06–43.42) 24.3–49.1 | 26.25 ABC (21.16–31.34) 16.4–38.0 | 16.87 AB (14.65–19.09) 13.1–22.1 | 10.49 AB (8.57–12.41) 7.1–14.7 | 3.19 A (2.83–3.55) 2.5–3.8 | 0.32 A (0.26–0.38) 0.20–0.47 | 631.69 AB (400.82–862.56) 211.5–1257.4 | 71.17 AB (45.42–96.92) 27.2–143.0 |
Miller Creek 2021 | 10 | 24.21 B (17.79–30.63) 14.4–42.6 | 17.68 C (12.81–22.55) 10.1–31.6 | 12.23 AB (10.13–14.33) 8.5–17.5 | 6.55 AB (4.95–8.14) 4.02–11.0 | 2.85 A (2.55–3.14) 2.1–3.4 | 0.46 A (0.39–0.53) 0.30–0.59 | 720.55 AB (413.86–1027.2) 275.8–1549.7 | 83.3 AB (48.09–118.51) 29.7–187.2 |
p-value | <0.0001 | <0.0001 | 0.0584 | 0.0386 | 0.2027 | 0.0780 | 0.0035 | 0.0074 |
Site and Year | Immune Responses | Thyroid Levels | EROD | Percent CV | |||||
---|---|---|---|---|---|---|---|---|---|
N | PIT54 | IgY | T3 Plasma | T4 Plasma | T3 Thyroid gland | T4 Thyroid gland | |||
Reference | |||||||||
Boulder Lake 2021 | 6 | 0.17 A 1 (0.14–0.20) 0.11–0.20 | 111.17 A (75.68–146.65) 86.9–174.2 | NA 2 | NA | 2.63 AB (2.05–3.21) 2.0–3.5 | 318.75 ABC (208.8–428.7) 188.1–459.7 | 17.78 B (11.16–24.39) 11.8–28.6 | 1.78 A (0.81–2.75) 0.4–2.8 |
North region | |||||||||
Rice Lake North 2021 | 5 | 0.14 A (0.12–0.16). 0.13–0.16 | 76.40 A (47.95–104.85) 41.3–96.9 | NA | NA | 3.30 A (2.76–3.84) 2.8–3.8 | 346.98 AB (271.2–422.8) 296.9–447.0 | 18.49 B (11.30–25.69) 8.75–23.38 | 2.52 A (1.60–3.44) 1.5–3.3 |
Martin Road 2021 | 4 | 0.13 A (0.08–0.19) 0.08–0.16 | 61.49 A (19.61–103.36) 33.9–91.4 | NA | NA | 1.68 AB (1.15–2.20) 1.3–2.0 | 225.58 ABCD (41.29–409.9) 59.6–317.0 | 9.79 B (4.79–14.79) 5.7–12.4 | 2.45 A (1.33–3.57) 1.7–3.1 |
ANG 2021 | 5 | 0.15 A (0.12–0.17) 0.12–0.18 | 103.06 A (61.40–144.72) 69.9–153.2 | NA | NA | 1.34 AB (0.241–2.44) 0.8–2.9 | 120.8 CD (0.257–241.3) 32.8–271.5 | 17.62 B (-1.39–36.63) 7.47–43.96 | 2.20 A (1.40–3.00) 1.5–3.0 |
UMD Farm 2021 | 1 | NA | 48.6 A | NA | NA | 0.9 B | 42.1 D | 5.05 B | 3.5 A |
St. Louis River | |||||||||
Thomson Reservoir 2019 | 10 | NA | NA | 0.60 A (0.38–0.81) 0.3–1.2 | 13.17 A (10.55–15.79) 7.5–19.7 | 3.04 A (2.66–3.43) 2.2–3.7 | 403.82 A (352.97–454.67) 273.8–494.6 | 31.66 AB (16.35–46.96) 8.6–69.7 | 2.36 A (1.62–3.10) 0.8–3.5 |
Thomson Reservoir 2021 | 10 | 0.13 A (0.11–0.15) 0.09–0.17 | 61.17 A (50.11–72.23) 39.0–85.9 | NA | NA | 2.57 AB (1.62–3.52) 1.5–6.0 | 357.9 AB (253.9–461.9) 177.1–651.8 | 13.50 B (9.25–17.75) 6.1–22.6 | 2.06 A (1.25–2.87) 0.6–3.9 |
Boy Scout Landing 2021 | 4 | 0.13 A (0.11–0.15) 0.11–0.14 | 72.66 A (33.02–112.30) 55.0–109.0 | NA | NA | 2.23 AB (1.61–2.84) 2.0–2.8 | 256.2 ABC (213.6–298.7) 221.3–279.9 | 12.54 B (5.21–19.86) 8.5–9.1 | 2.03 A (0.98–3.07) 1.2–2.8 |
Munger Landing 2019 | 5 | NA | NA | 0.572 A (0.34–0.81) 0.42–0.9 | 13.06 A (10.79–15.33) 10.4–15 | 2.844 AB (0.57–5.12) 1.23–4.98 | 222.8 ABCD (97.27–348.33) 120.4–349.2 | 98.50 A (-11.88–208.9) 27.72–243.41 | 3.06 A (1.40–4.72) 1.1–4.6 |
Munger Landing 2021 | 7 | 0.152 A (0.12–0.19) 0.091–0.199 | 76.132 A (49.44–102.83) 37.7–125.8 | NA | NA | 2.157 AB (1.70–2.61) 1.5–3 | 276.7 ABC (201.3–352.0) 215.6–439.8 | 21.622 B (13.81–29.43) 8.14–32.21 | 2.014 A (1.26–2.77) 1.1–3.5 |
Stryker Bay 2019 | 10 | NA | NA | 0.557 A (0.45–0.66) 0.3–0.78 | 15.58 A (13.12–18.04) 9.2–20.1 | 2.715 AB (2.05–3.38) 1.56–4.23 | 199.69 ABCD (134.45–264.93) 126.8–434.5 | 35.447 AB (26.73–44.16) 10.49–53.52 | 3.03 A (2.44–3.62) 1.6–4 |
Erie Ponds 2019 | 9 | NA | NA | 0.47 A (0.37–0.57) 0.33–0.68 | 11.411 A (9.35–13.48) 7.9–16 | 2.226 AB (1.86–2.60) 1.44–2.78 | 181.066 BCD (132.85–229.29) 81.5–286.2 | 62.638 AB (17.91–107.37) 10.75–186.59 | 2.3 A (1.65–2.95) 1.4–4.1 |
Erie Ponds 2021 | 10 | 0.145 A (0.13–0.16) 0.112–0.193 | 88.105 A (63.44–112.77) 38.4–134.7 | NA | NA | 2.57 AB (1.91–3.23) 1.7–4.7 | 296.76 ABC (263.0–330.6) 233.5–385.3 | 37.083 AB (30.65–43.52) 21.18–50.11 | 2.38 A (1.73–3.03) 0.8–3.4 |
Miller Creek 2021 | 10 | 0.119 A (0.10–0.14) 0.068–0.179 | 86.445 A (57.24–115.65) 34.45–188.8 | NA | NA | 2.25 AB (1.81–2.69) 1.4–3.6 | 139.64 CD (105.8–173.5) 80.1–215.3 | 27.182 B (18.43–35.94) 11.42–58.68 | 2.5 A (1.48–3.52) 0.5–5.3 |
p-value | 0.1193 | 0.0807 | 0.6068 | 0.0555 | 0.0128 | <0.0001 | <0.0001 | 0.4584 |
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Custer, C.M.; Dummer, P.M.; Etterson, M.A.; Haselman, J.T.; Schultz, S.; Karouna-Renier, N.; Matson, C. Per- and Polyfluoroalkyl Substances in the Duluth, Minnesota Area: Exposure to and Biomarker Responses in Tree Swallows Relative to Known Fire-Fighting Foam Sources. Toxics 2024, 12, 660. https://doi.org/10.3390/toxics12090660
Custer CM, Dummer PM, Etterson MA, Haselman JT, Schultz S, Karouna-Renier N, Matson C. Per- and Polyfluoroalkyl Substances in the Duluth, Minnesota Area: Exposure to and Biomarker Responses in Tree Swallows Relative to Known Fire-Fighting Foam Sources. Toxics. 2024; 12(9):660. https://doi.org/10.3390/toxics12090660
Chicago/Turabian StyleCuster, Christine M., Paul M. Dummer, Matthew A. Etterson, Jonathan T. Haselman, Sandra Schultz, Natalie Karouna-Renier, and Cole Matson. 2024. "Per- and Polyfluoroalkyl Substances in the Duluth, Minnesota Area: Exposure to and Biomarker Responses in Tree Swallows Relative to Known Fire-Fighting Foam Sources" Toxics 12, no. 9: 660. https://doi.org/10.3390/toxics12090660