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Supporting Information For:
Atmospherically Deposited PBDEs, Pesticides, PCBs, and PAHs in Western US National
Park Fish: Concentrations and Consumption Guidelines
Luke K. Ackerman, Adam R. Schwindt, Staci L. Simonich*, Dan C. Koch, Tamara F. Blett,
Carl B. Schreck, Michael L. Kent, Dixon H. Landers
Number of Pages: 13
Number of Tables: 4
Number of Figures: 3
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Experimental
Chemicals
All solvents were Optima grade from Fisher Scientific (Fairlawn, NJ). Anhydrous sodium
sulfate was Mallinckrodt Baker (Phillipsburg, NJ) pesticide grade. Isotopically NONlabeled chemical standards (natives) in mixes and individually were purchased from, the
EPA repository, Chem Services Inc. (West Chester, PA), Restek (Bellefonte, PA), SigmaAldrich Corp. (St. Louis, MO), AccuStandard (New Haven, CT), or Cambridge Isotope
Labs (Andover, MA). Isotopically labeled standards were purchased from CDN Isotopes
(Pointe-Claire, Quebec, Canada) or Cambridge Isotope Labs (Andover, MA). The
isotopically-labeled recovery surrogates were d10-fluorene, d10-phenanthrene, d10-pyrene,
d12-triphenylene, d12-benzo[a]pyrene, d12-benzo[ghi]perylene, d14-EPTC, d5-atrazine, d10diazinon, d7-malathion, d10-parathion, d8-p,p’-DDE, d8-p,p’-DDT, d6-methyl parathion, d13alachlor, d11-acetochlor, 13C12-PCB 101 (2,2’,4,5,5’-pentachlorobiphenyl), 13C12-PCB 180
(2,2’, 3,4,4’,5,5’-heptachlorobiphenyl), d10 - chlorpyrifos, 13C6-HCB, d6- -HCH, d4endosulfan I, d4-endosulfan II , d14-trifluralin, 13C12-BDE 28 (2,4,4’-tribromodiphenyl ether),
13
C12-BDE 47 (2,2’,4,4’-tetrabromodiphenyl ether), 13C12-BDE 99 (2,2’,4,4’,5tetrabromodiphenyl ether), 13C12-BDE 100 (2,2’,4,4’,6-tetrabromodiphenyl ether), 13C12BDE 118 (2,3’,4,4’,5-tetrabromodiphenyl ether), 13C12-BDE 138 (2,2’,3,4,4’,5’tetrabromodiphenyl ether), 13C12-BDE 153 (2,2’,4,4’,5,5’-tetrabromodiphenyl ether), and
13
C12-BDE 183 (2,2’,3,4,4’,5’,6-tetrabromodiphenyl ether). The isotopically-labeled
internal standards were d10-acenaphthene, d12-benzo[k]fluoranthene, d10-fluoranthene, and
13
C12-PCB 138 (2,2’,3,4,4’,5’-hexachlorobiphenyl). All standards were stored at 4°C and
remade as needed, or at least once a year to insure stability. The organophosphate standards
were stored separately from other chemical classes in ethyl acetate (EA) to minimize
degradation. All lab ware was washed, rinsed, covered in foil, baked at 345 C for 12hrs, and
solvent-rinsed prior to use.
Samples
Standard Reference Material (SRM) #1946 Lake Superior Lake Trout was purchased from
the National Institute of standards and Technology (NIST) (Gaithersburg, MD).
Representative fish samples for method detection limit and recovery studies were collected
from remote lakes of US National Parks, specifically Wonder Lake, Denali NP, AK,
Emerald Lake, Sequoia NP, CA, and Mills Lake, Rocky Mountain NP, CO. Most fish were
caught with hook and line, stored in 8 gall buckets with lake water for less than 30 min prior
to euthanasia and field dissection. Gill-nets and set lines were employed for the collection
of some fish from Denali National Park. Upon capture ~100uL of blood was removed from
the caudal vein for hormone, biomarker, and hematological analysis, and the fish was
euthanized, weighed, and fork length measured. A quick field dissection to obtain
pathological slices of kidney, spleen, liver, gills, and gonads was performed on solvent
rinsed and baked foil with solvent rinsed scalpels and forceps. Gut contents were evacuated,
and the carcass was wrapped in foil or aluminized poly-bags, double-bagged, and shipped to
the laboratory on dry ice. Field blanks of the collection procedure without a fish were also
obtained. When received at the lab the samples were logged into a -25 °C freezer until
analysis.
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Sample Preparation
Whole fish carcasses were homogenized in liquid nitrogen inside a Blixer BX-6 5HP
stainless steel food processor with polycarbonate lid until a fine, frozen slurry of nitrogen
and fish homogenate was obtained. Personal protective equipment included face shields and
cold gloves. Frozen homogenate was transferred to cleaned jars, sealed, weighed, and stored
at -25 °C, until extraction. Method blanks were obtained by grinding 150 g clean sodium
sulfate with the liquid nitrogen and processing samples through the method. A 1-2 g
subsample of the fish homogenate was gravimetrically analyzed for moisture content by
baking for 24 hrs at 105 °C and re-weighing (until stable).
Sample Extraction
Samples and method blanks (~20g fish, 1.8g SRM) were weighed out onto a clean tarred
glass mortar with a bed of clean sodium sulfate, sodium sulfate was added and the mixture
ground until free flowing (<10min). The fish sodium sulfate mixture was transferred into
100mL stainless steel Accelerated Solvent Extractor (ASE) cells (Dionex, Sunnyvale, CA)
with each cell containing ~120 g of the fish/sodium sulfate mixture. Once in the ASE cells,
12.5-150ng of isotopically labeled recovery surrogates in 1.25-10 ng/uL solutions were
distributed equally among the tops of the cells containing sample or blank. The cells were
capped. The sample or blank was extracted using dichloromethane (DCM) (100 °C, 1500
psi, 2 cycles of 5 minutes, 150 % flush volume). The extract was dried with clean sodium
sulfate, decanted and filtered with glass wool into a 500mL volumetric flask, which was
filled to the mark. Gravimetric lipid analysis was performed on 2% of the sample by heating
the evaporated 10ml extract sub-sample at 105 °C for one hour and weighing the extracted
lipid that remained (until stable). The remainder of the extract was concentrated to 0.5 mL in
the TurboVap II (Zymark, Hopkinton, MA) with nitrogen, and solvent exchanged to hexane.
Polar matrix interferences were removed by loading the hexane extract on a 20 g silica solid
phase extraction (SPE) cartridge (Mega Bond Elut Varian). Analytes were eluted from the
silica SPE using 25mL hexane, 25 mL 60:40 hexane:DCM, and 75 mL 70:30DCM:hexane.
The combined eluate was then concentrated and solvent exchanged to DCM. Elemental
sulfur and the high molecular weight interferences were removed using a Waters Gel
Permeation Chromatography (GPC) Cleanup System (Milford, MA). The target fraction
was concentrated to 0.3 mL with ethyl acetate rinses under a gentle stream of nitrogen and
spiked with 15 µL of a 10 ng/µL isotopically labeled internal standard solution. Blank
extracts were carried through the entire method together with batches of 3 to 5 samples.
GC/MS Analysis
In general extracts were analyzed by gas chromatographic mass spectrometry (GC/MS) on
an Agilent 6890 GC coupled with an Agilent 5973N MSD, using both electron impact (EI)
ionization and electron capture negative ionization (ECNI) modes. The ECNI compounds
monitored, their SIM windows, and characteristic ions are listed in Table S2. Analysis was
attempted for a larger list of compounds than that for which the method was subsequently
validated. One microliter of the 0.3 mL extract was injected in pulsed splitless mode with a
HP 7683 auto-sampler. The inlet was a 2 mm id glass gooseneck with wool, at 300 °C (pulse
of 20 psi until 0.6 min). Chromatographic separations were achieved on a DB-5MS column
(J&W Scientific, 30m x 0.25 mm id.; 0.25 Rm film thickness) with helium carrier gas
flowing at 0.9 mL/min. The GC oven temperature program used for the GC/EI-MS was
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reported previously and the program for the ECNI/MS was modified as follows to permit
quantitation of the PBDEs: 120 °C for 1 min, ramped at 4 °C/min to 275 °C, ramp 6 °C to
320, held 6.75 min for a total runtime of 54 minutes.
QA/QC
Internal standard calibration curves were prepared from standard solutions, ranging 2.5
fg/uL to 5 ng/uL. A minimum of 5 calibration points (S3 per order of magnitude) were
included in every curve and the curve was required to yield an r2 >0.98, or less than 15%
deviation at every point. Calibration accuracy was checked with a low level calibration
solution at a frequency of at least 18%, and the instrument re-calibrated as needed.
Calibration solutions were re-prepared at least once a year or as needed. Duplicate injections
were performed at a frequency of 10% and duplicates with >25 % relative deviation were
flaged and re-run as needed. Standard reference material was analyzed at a frequency of
10%. Target compounds were identified only when the following criteria were met: a peak
of greater than 3:1 S:N was observed for all three characteristic ions within 0.01 min or one
scan of each other, the quantitation ion peak matched standard RT within 0.05 min, and the
relative response of the three ions was within 20% of standards’ relative responses. Sample
values were flagged if the lab blank was greater than 5% of the sample analyte mass, the
field blank greater than 20%, the calibration check >30% deviation, or if the recovery
surrogate yielded >130% or <30% recovery. Quantitation values were later censored
according to method detection and quantitation limits. The method quantitation limit was set
as the mass of the lowest concentration calibration solution used for each curve, normalized
to each sample’s mass extracted. If the mass in any blank was greater than 33% of the
corresponding sample’s mass, the sample value was deleted and flaged. All reported values
have been blank subtracted and recovery corrected.
Results
The following compounds were detected in less than 20% of the samples and less than 50%
of the samples from any single lake: b-HCH, d-HCH, heptachlor, aldrin, endrin, endrinaldehyde, PCB 74, BDEs #10, 7, 8, 12, 13, 15, 30, 32, 17, 25, 35, 37, 75, 71, 66, 77, 119,
116, 126, 118, 138, 166, 181, 190, triallate, chlorpyrifos oxon, etridiazole, parathion, ethion,
and all PAHs.
-4-
Table S1. Average Fish Sample and Site Characteristics
Lake
US National Park
1) Emerald
Sequoia-Kings Canyon
2) Pear
Sequoia-Kings Canyon
3) LonePine
Rocky Mountain
4) Mills
Rocky Mountain
5) LP19
Mt. Rainier
6) Golden
Mt. Rainier
7) Hoh
Olympic
8) PJ
Olympic
9) Oldman
Glacier
10) Snyder
Glacier
11) McLeod
Denali
12) Wonder
Denali
13) Matcharak
Gates of the Arctic
14) Burial
Noatak National Preserve
Latitude
(dd)
36.58
36.60
40.22
40.29
46.82
46.89
47.90
47.95
48.50
48.62
63.38
63.48
67.75
68.43
Longitude Elevation
(dd)
(m)
118.67
118.67
105.73
105.64
121.89
121.90
123.79
123.42
113.46
113.79
151.07
150.88
156.21
159.18
2810
2908
3018
3030
1372
1369
1379
1384
2026
1597
564
605
502
430
Fish Species
brooktrout
brooktrout
brooktrout
rainbow trout
brooktrout
brooktrout
brooktrout
brooktrout
cutthroat trout
cutthroat trout
burbot, whitefish
lake trout
lake trout
lake trout
5
Length mass
(mm)
(g)
199
201
244
231
237
225
206
197
382
179
237
457
508
411
73
75
141
153
122
110
82
67
596
57
110
1040
1410
768
Age
(yr)
5.2
5.2
4.7
3.9
5.0
4.3
8.1
5.5
3.6
4.6
3.5
19.3
19.5
16.9
Growth Condition Sex
Factor
Ratio
Rate
3
(g/yr)
(cg/cm ) (M:F)
16
0.91
1.5
17
0.94
4.0
33
0.95
1.5
47
1.19
0.7
29
0.92
1.0
27
0.97
2.3
13
0.94
1.0
15
0.90
1.0
167
1.03
1.5
13
0.97
1.0
24
0.62
2.0
57
1.09
1.5
74
1.03
1.0
43
0.96
1.0
Date
Sampled
n
08/24/03
08/25/03
09/13/03
09/08/03
08/08/05
08/13/05
09/08/05
09/13/05
08/19/05
08/23/05
08/10/04
08/12/04
08/01/04
08/02/04
10
10
10
10
10
10
10
10
10
10
4,2
10
10
10
Total
136
1
2
3
4
Figure S1 – Map of National Parks/Preserves Sampled
1
Table S2. ECNI Target Analytes, Surrogates, Internal Standards, & SIM Windows
Analytes,
& Surrogates
Surrogate for
Quantitation
13
d14 Trifluralin
Trifluralin
HCH, alpha
13
d14 Trifluralin
d6 gamma-HCH
13
C6-HCB
HCB
13
Retention Time
(min)
SIM Window 1
13.69
C12 PCB 138
13.90
Quantiation
Ion m/z
Confirmation
Ion m/z
2nd Confirmation
Ion m/z
349.2
350.2
319.2
335.1
336.1
305.1
SIM Window 2
14.61
71.0
73.0
70.0
14.69
291.8
293.8
289.9
14.70
283.8
285.8
281.8
C12 PCB 138
C6 HCB
SIM Window 3
15.94
71.0
73.0
70.0
16.01
72.0
74.0
263.0
d6 gamma-HCH
16.19
71.0
73.0
70.0
HCH, delta
d6 gamma-HCH
SIM Window 4
17.70
71.0
252.9
254.9
Triallate
d6 gamma-HCH
17.72
160.0
161.1
104.1
HCH, beta
d6 gamma-HCH
d6 gamma-HCH
HCH, gamma
PBDE #10
13
13
Metribuzin
C12 PBDE 28
d6 gamma-HCH
Heptachlor
d6 gamma-HCH
C12 PCB 138
SIM Window 5
19.05
167.1
80.9
78.9
19.15
198.1
199.1
184.1
19.61
265.9
267.9
299.9
C12 PBDE 28
20.51
167.1
80.9
78.9
Chlorpyrifos oxon
d10 Chlorpyrifos
d10 Chlorpyrifos
SIM Window 6
21.14
297.0
298.0
299.0
21.19
322.0
324.0
214.0
Aldrin
d6 gamma-HCH
21.24
167.1
78.9
80.9
21.28
237.0
239.0
329.9
PBDE 7
PBDE #8
Chlorpyrifos
Dacthal
13
13
C12 PCB 138
13
C12 PBDE 28
d10 Chlorpyrifos
d6 gamma-HCH
21.37
313.0
315.0
214.0
SIM Window 7
21.54
332.0
330.0
334.0
PBDE 12
13
C12 PBDE 28
21.65
167.1
80.9
78.9
PBDE 13
13
C12 PBDE 28
21.79
167.1
80.9
78.9
PBDE 15
13
C12 PBDE 28
22.33
167.1
80.9
78.9
Chlordane, oxy
d4 Endosulfan I
SIM Window 8
23.12
423.9
425.9
351.9
Heptachlor epoxide
d4 Endosulfan I
23.13
389.8
387.8
391.8
13
C12 PCB 101
23.28
291.9
293.9
289.9
d4 Endosulfan I
SIM Window 9
24.26
409.9
407.9
411.8
PCB 74
Chlordane, trans
PBDE 30
13
C12 PBDE 28
13
C12 PCB 101
PCB 101
d4 Endosulfan I
13
SIM Window 10
24.67
246.9
80.9
78.9
337.9
335.9
339.9
13
C12 PCB 138
24.68
24.69
325.9
327.9
323.9
13
C12 PCB 138
24.72
377.9
375.9
373.9
C12 PCB 101
Endosulfan I
d4 Endosulfan I
24.82
403.9
371.9
369.9
Chlordane, cis
d4 Endosulfan I
24.83
265.9
263.9
267.9
d4 Endosulfan I
SIM Window 11
24.98
443.8
445.8
441.8
d4 Endosulfan I
SIM Window 12
26.07
345.9
347.9
379.9
C12 PBDE 28
26.56
246.9
80.9
78.9
d4 Endosulfan II
SIM Window 13
27.03
Nonachlor, trans
Dieldrin
PBDE 32
13
345.9
347.9
379.9
PBDE 17
13
C12 PBDE 28
27.15
246.9
80.9
78.9
PBDE 25
13
C12 PBDE 28
27.20
246.9
80.9
78.9
Endrin
1
Internal Standard
for Quantitation
2
Table S2. ECNI SIM Windows continued….
SIM Window 14
27.51
C12 PCB 138
27.55
411.9
413.9
409.9
325.9
327.9
323.9
27.56
405.9
407.9
371.9
SIM Window 15
27.79
443.8
445.8
441.8
27.90
338.8
78.9
80.9
C12 PBDE 28
27.90
326.9
78.9
80.9
Endosulfan II
SIM Window 16
28.24
379.9
381.9
345.9
C12 PBDE #28
28.42
326.9
78.9
80.9
28.48
359.9
361.9
357.9
C12 PBDE 28
29.02
326.9
78.9
80.9
d4 Endosulfan II
SIM Window 17
29.33
385.9
387.9
421.8
29.65
360.0
362.0
358.0
29.65
371.9
369.9
373.9
13
d4 Endosulfan II
PCB 118
Endosulfan II
Nonachlor, cis
13
C12 PBDE 28
PBDE 28
Endrin aldehyde
PBDE 35
C12 PCB 180
Internal Standard
C12 PCB 180
SIM Window 18
30.29
393.9
359.9
397.9
PCB 183
13
C12 PCB 180
30.54
393.9
359.9
397.9
PBDE 75
13
C12 PBDE 47
31.72
324.9
78.9
80.9
C12 PBDE 47
SIM Window 19
32.33
324.9
78.9
80.9
405.9
407.9
409.9
C12 PCB 180
PBDE 47
13
13
C12 PCB 138
32.60
32.95
324.9
78.9
80.9
13
C12 PCB 138
32.95
336.7
78.9
80.9
SIM Window 20
33.76
404.8
78.9
80.9
C12 PCB 180
34.10
367.8
369.8
403.8
C12 PBDE 47
35.10
325.9
78.9
80.9
C12 PBDE 100
SIM Window 21
36.61
404.8
78.9
80.9
36.61
37.10
37.78
416.7
404.8
404.8
78.9
78.9
78.9
80.9
80.9
80.9
13
C12 PBDE 47
C12 PBDE 47
PBDE 66
13
Mirex
13
PBDE 66
13
C12 PBDE 100
PBDE 119
PBDE 99 L
C12 PBDE 99
PBDE 116
13
13
13
C12 PCB 138
13
C12 PCB 138
C12 PBDE 99
37.79
416.7
78.9
80.9
C12 PBDE 99
38.21
404.8
78.9
80.9
C12 PBDE 118
SIM Window 22
38.78
405.8
78.9
80.9
38.78
417.7
78.9
80.9
C12 PBDE 99
SIM Window 23
39.79
80.9
13
13
C12 PBDE 47
13
C12 PBDE 118
13
C12 PCB 138
403.8
78.9
PBDE 155
13
C12 PBDE 153
39.80
643.5
78.9
80.9
PBDE 126
13
C12 PBDE 153
40.21
403.8
78.9
80.9
PBDE 154
13
C12 PBDE 153
SIM Window 24
40.63
482.7
78.9
80.9
PBDE 153 L
13
C12 PBDE 153
42.08
403.8
78.9
80.9
42.08
415.6
78.9
80.9
C12 PBDE 153
PBDE 138
PBDE 166
PBDE 183 L
1
C12 PCB 180
13
PBDE 85/155
13
13
C12 PCB 138
PCB 187
PBDE 118 L
13
d4
13
13
PBDE 100 L
13
13
PBDE 37
PBDE 49
13
13
C12 PCB 138
13
13
d4 Endosulfan II
13
PCB 138
13
C12 PCB 101
d4 Endosulfan II
PCB 153
Endosulfan sulfate
13
13
C12 PBDE 183
PBDE 181
PBDE 190
13
C12 PCB 138
13
C12 PBDE 153
43.77
401.8
78.9
80.9
13
C12 PBDE 153
43.93
401.8
78.9
80.9
C12 PBDE 183
SIM Window 24
45.51
481.7
78.9
80.9
45.51
493.6
78.9
80.9
13
13
C12 PCB 138
13
C12 PBDE 183
47.20
481.7
78.9
80.9
13
C12 PBDE 183
47.51
481.7
78.9
80.9
3
1
2
3
4
5
Figure S2. Representative Final Fish Extract Selected Ion Chromatograms
4
Table S3.Fish analytical method recovery, estimated method
detection limits, accuracy, and precision
Compounds
Method
Recovery1
(%)
Estimated
Method
Detection
Limit2
(pg/g ww)
Determined
Values for
NIST SRM
1946
(ng/g ww)
Avg.
Avg.
Avg.
Log
Kow
SD
RSD
%
RSD
Deviation
from
Certified
Values3
(%)
% Diff
%
Method Averages
Median
Average
Min
Max
6.1
6.1
2.6
9.4
59.3
61.4
31.4
98.3
3.5
4.1
0.3
12
18
79
0.2
920
3.3
11
0.83
86
7.5
30
0.10
350
9.7
15
0.22
66
0.0
7.1
0
30
1.0
5.4
0.46
46
6.5
34
0
0
5.3
4.7
0.38
6.6
0.91
16
34
31
12
90
1.8
9.7
49
1.1
0.22
37
2.7
15
7.9
4.8
8.9
9.0
7.1
25
66
5.9
0
0
0
15
0
0
30
9.5
17
16
16
28
0
0
0
Organochlorines Pesticides & Metabolites
HCH, gamma
HCH, alpha
HCH, beta
HCH, delta
Methoxychlor
Heptachlor epoxide
Endrin
Heptachlor
Hexachlorobenzene
o,p'-DDE
Chlordane, oxy
Dieldrin
Chlordane, cis
p,p'-DDD
Nonachlor, trans
o,p'-DDD
Chlordane, trans
Nonachlor, cis
Aldrin
o,p'-DDT
p,p'-DDE
Mirex
p,p'-DDT
3.8
3.8
4.0
4.1
4.5
4.6
5.2
5.2
5.5
5.5
5.5
5.5
5.9
5.9
6.1
6.1
6.1
6.4
38.2
37.6
44.3
42.2
62.1
33.6
89.1
48.5
37.8
53.8
35.1
95.3
32.6
67.8
32.0
55.2
31.4
40.3
1.6
1.6
1.7
1.7
1.8
2.0
2.2
1.3
1.9
2.1
1.9
3.6
1.0
1.0
1.0
2.1
1.0
1.5
17
0.2
7.8
0.6
99
14
170
1.6
5.0
58
5.5
8.4
16
99
2.9
68
1.6
5.0
7.5
8.1
1.7
3.0
73
2.2
26
1.42
1.9
23
1.9
21
6.8
39
1.3
16
0.96
1.0
6.5
39.4
1.6
21
3.5
6.8
6.9
6.9
6.9
61.1
63.7
54.0
68.1
4.8
4.7
3.3
2.1
97
98
6.8
94
63
12
1.5
50
16
350
6.1
34
20
9.3
3.2
6.1
0.44
0.10
12
10
4.6
11
4.1
28
134
110
51
23
54
20
29
33
30
6.2
8.6
13
OrganochlorineSulfide Pesticides & Metabolites
Endosulfan sulfate
Endosulfan I
Endosulfan II
3.7
4.7
4.8
46.4
36.0
49.0
4.0
3.2
3.5
3.7
4.9
8.9
0.83
2.46
5.8
44.4
48.8
45.5
9.6
10.5
8.9
9.1
1.9
5.5
1.0
2.59
0.88
34.8
62.2
88.0
42.9
1.8
2.2
2.3
3.4
15
2.6
11
7.2
2.2
1.6
1.80
0.89
78.9
66.5
77.3
65.0
74.5
75.9
77.3
1.2
4.5
5.7
4.6
6.1
5.3
5.0
48
1.1
2.6
2.2
2.2
0.84
1.4
15
2.6
2.9
0.87
0.96
3.7
2.2
Phosphorothioate Pesticides
Parathion
Ethion
Chlorpyrifos
3.8
5.1
5.1
Miscellaneous Pesticides
Etridiazole
Dacthal
Triallate
Trifluralin
2.6
4.3
4.6
5.3
PolyChlorinated Biphenyls
1
2
PCB 74
PCB 101
PCB 138
PCB 153
PCB 118
PCB 183
PCB 187
6.3
6.4
6.7
6.9
7.0
8.3
7.2
15
20
21
0
0
0
0
1 - @8ng/g spike, n=3; 2 - n=3; 3 - Values within NIST confidence intervals = 0% diff
5
Table S3.Fish analytical method performance, continued…
Compounds
Log
Kow
Method
1
Recovery
(%)
Estimated
Method
Detection
Limit2
(pg/g ww)
Determined
Values for
NIST SRM
1946
(ng/g ww)
Avg.
Avg.
Avg.
SD
RSD
%
RSD
Deviation
from
Certified
Values3
(%)
% Diff
%
Polycyclic Aromatic Hydrocarbons
Acenaphthylene
Acenaphthene
Fluorene
Anthracene
Phenanthrene
Pyrene
Fluoranthene
Chrysene /Triphenylene
Benzo(a)anthracene
Retene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(b)fluoranthene
Indeno(1,,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(e)pyrene
Benzo(ghi)perylene
3.9
4.0
4.2
4.5
4.5
5.1
5.2
5.7
5.9
6.4
6.5
6.5
6.6
6.7
6.8
6.9
7.0
36.0
54.4
41.7
51.8
56.3
63.7
58.4
59.3
59.4
55.3
64.6
43.4
64.4
60.5
58.0
57.8
60.1
PolyBrominated Diphenyl Ethers
1
2
BDE 10
BDE 7
BDE 8
BDE 12
BDE 13
BDE 15
BDE 30
BDE 32
BDE 17
BDE 25
BDE 28
BDE 35
BDE 37
BDE 75
BDE 49
BDE 71
BDE 47
BDE 66
BDE 77
BDE 100
BDE 119
BDE 99
BDE 116
BDE 85/155
BDE 126
BDE 118
BDE 155
BDE 154
BDE 153
BDE 138
BDE 166
BDE 183
BDE 181
BDE 190
5.0
5.0
5.0
5.8
5.8
5.8
5.9
5.9
5.8
5.9
5.9
6.7
6.7
6.8
6.8
6.8
6.8
6.8
7.6
7.7
7.7
7.7
7.7
7.7 / 8.6
8.5
7.7
8.6
8.6
8.6
8.6
8.6
9.4
9.4
9.4
64.2
49.7
52.0
45.2
50.4
82.2
47.2
46.9
55.7
55.9
51.1
52.6
52.3
86.9
94.1
84.8
91.1
83.6
93.6
79.0
78.9
85.7
75.6
91.8
88.6
75.0
80.8
79.7
78.6
81.6
98.3
81.5
76.8
72.4
2.5
5.5
1.6
5.4
3.8
5.4
4.0
0.9
2.3
5.8
0.3
5.2
0.9
0.3
1.6
0.7
0.7
38
50
16
59
56
6.7
7.6
20
26
44
23
17
20
18
19
100
6.3
4.1
2.5
1.7
6.8
10
3.5
1.8
12
0.96
14
0.9
1.7
1.6
3.33
8.9
34
1.3
6.4
2.4
5.3
2.3
2.7
6.3
6.6
2.2
2.4
2.3
2.1
2.0
2.1
6.7
7.1
5.2
7.5
8.5
8.0
8.4
7.2
6.3
7.9
8.3
9.2
11.9
7.0
7.4
6.7
7.1
7.8
5.8
4.1
5.0
920
120
710
880
910
860
240
38
32
43
23
57
40
24
30
22
14
120
83
6.7
19
23
91
37
36
200
2.3
8.3
6.5
1.1
1.9
1.6
3.5
5.0
26
43
23
18
21
15
37
7.6
8.4
7.1
2.8
3.8
8.1
5.3
3.6
1.9
1.1
26
24
1.1
14
1.95
48
10
9.2
86
1.0
2.7
3.1
1.1
1.7
0.95
3.14
2.5
4
0.94
1.9
29
10
26
0
n/a
8.4
2.7
0
18
5.4
0
0.68
6.2
2.9
11
18
9.3
0
0
0.23
14
5
1 - @8ng/g spike, n=3; 2 - n=3; 3 - Values within NIST confidence intervals = 0% diff
6
1
2
3
4
5
Figure S3 - Concentrations of select current (A,B) and historic use contaminants (C,D) in
average (bars) & individual fish (symbols) from western US national park lakes compared to
estimated non-cancer (A,B) and cancer (C,D) health thresholds for recreational fishing. * nd>50% of lake fish.
7
1
2
3
4
8