1
Supplemental Data
Spatial Patterns of Atmospherically Deposited Organic Contaminants at high elevation in
the Southern Sierra Nevada Mountains, California
David F. Bradford, Kerri Stanley, Laura L. McConnell, Nita G. Tallent-Halsell, Maliha S. Nash,
and Staci M. Simonich
Passive Air Sample Sampling and Analysis Method
Media Preparation. Pre-cut polyurethane foam (PUF) disks (13.5 cm diam., 1.2 cm thick)
were purchased from Shawnee Instruments, Inc. (Village of Cleves, OH). Other characteristics
of the PUF disks used in the study were: bulk density, 2.5 x 104 g/m3; volume, 1.7 x 10-4 m3;
surface area, 3.4 x 10-2 m2. PUF disks were pre-cleaned prior to deployment. The PUF material
was rinsed well with distilled water, extracted using a Soxhlet apparatus using chromatographicgrade acetone for 24 hours, followed by a second extraction with chromatographic-grade ethyl
acetate (Fisher Scientific, Newark, DE). The PUF disks were then dried in a vacuum oven at
approximately 30 oC for 48 hours. Disks were stored in bulk in a large clean, air-tight glass jar
and protected from light exposure until needed.
Prior to deployment, each PUF disk was spiked with 25 mL of depuration-chemical
mixed standard solution in order to assess the air-side mass transfer coefficient, ka. Disks were
placed on clean aluminum foil inside a fume hood, and a glass volumetric pipette was used to
apply the solutions over the entire disk. The large volume was used to thoroughly saturate the
disk. The disks were allowed to dry in the fume hood for approximately 3 minutes on each side
prior to placing each disk into a separate clean glass jar with a Teflon-lined lid. Spiked disks
were kept at ≤ -20 oC (either in a freezer or kept on dry ice) until deployment to minimize
2
degradation of the depuration chemicals. Three deuterated compounds with a large range of
octanol-air partition coefficients (KOA) values were used: 13C6-hexachlorobenzene, diazinon-d10
diethyl, and d4-α-endosulfan (Table S2).
Extraction and Analysis. Samples were extracted in batches of approximately 20. With
each batch, two laboratory controls were included: a laboratory blank PUF disk and a spike PUF
disk. The spike PUF disk consisted of a clean PUF disk spiked with a mixture of
organophosphorus and organochlorine compounds as well as five polybrominated diphenyl
ethers (PBDEs; Table S2). Concentrations in the spike solutions ranged from 1.00 ng/µL for
most of the organochlorine compounds and PBDEs; 2.00 ng/µL for the 4,4’-DDE and 4,4’-DDD;
and 4.00-5.00 ng/µL for the organophosphorus compounds, diazinon and malathion. One
hundered microliters of a second solution containing 100 ng/µL of 13C6-hexachlorobenzene,
diazinon-diethyl d10 and d4-α-endosulfan were also spiked onto the PUF disk control sample.
All samples were extracted using a Soxhlet apparatus for eight hours. The extracts were
reduced to approximately 15 mL using rotary evaporation. Extracts were further reduced to 1
mL using the N-EVAP nitrogen evaporator and then exchanged into isooctane as a final solvent.
Extraction was followed by a clean-up of the extract using two solid-phase extraction (SPE)
cartridges in series. The first cartridge was a 6-mL reservoir, Supelclean LC-Alumina-N
cartridge (Supelco, Bellefonte, PA) with approximately 0.5 cm-thick layer of pre-extracted
sodium sulfate (Fisher Scientific, Newark, DE). The second cartridge was a 10-mL reservoir,
SPEC-SI filter cartridge with 35 mg of silica resin (Varian Chromatography, Lake Forest, CA).
The cartridges were pre-eluted with 6 mL of hexane which was discarded. The sample extract
was then loaded onto the sodium sulfate column and eluted with 6 mL of a 4:1 hexane:petroleum
ether mixture followed by 6 mL of ethyl acetate. The eluant was captured in a 15-mL conical
3
centrifuge tube. The sample was then concentrated using the N-EVAP to approximately 1 mL
and then exchanged into isooctane as a final solvent. An octachlorinated biphenyl,
2,2',3,4,4',5,6,6'-octachlorobiphenyl, was added to the final extracts and used as an internal
standard for quantitative analysis.
Samples were analyzed using an Agilent 6890 gas chromatograph coupled to a 5975 inert
mass spectrometer. Selected-ion-monitoring was used, and the mass spectrometer was operated
in NCI mode. Methane was the ionization gas at a pressure of 40 Pa. The source and quadrapole
temperatures were 150°C. Gas chromatography parameters for monitored compounds were as
follows: 30-m DB-17 MS capillary column (J&W Scientific Corporation, Folsom, CA), 0.25mm inner diameter, 0.25-µm film thickness, helium carrier gas, constant flow at 1.0 mL/min;
temperature program: injector port temperature 250°C, initial temperature 130°C, hold 1.0 min,
6°/min to 205°C, hold 4.5 min, 6°/min to 300, hold 4.5 min. The injection port was operated in
pulsed splitless mode. Pressure was 44 kPa with a pulse pressure of 275 kPa. The detector
interface was 300°C.
A five-point calibration curve was established for each analyte and instrument response
was linear over the calibration standards range (r2 ≥ 0.99). Calibration standard concentrations,
on average, ranged from 0.010 ng/µL to 0.203 ng/µL. The instrument was recalibrated every 20
to 25 sample injections. Quantitation of each compound was calculated based on the area of the
ion with the largest abundance. Confirmation of a particular compound in a sample was
determined by the presence of at least one of the two qualifying ions in the proper ratio to the
quantifying ion (± 20%) and the retention time of the peak was within ±0.02 min of the retention
time of the standard solution. The requirement for only one qualifying ion in the proper ratio is
4
due to the use of the NCI mode where the number of ions in the mass spectra is often
dominated by one or two ions, with very small contributions from other ions.
Estimated detection limits (EDLs) were determined for each analyte as suggested by the
U.S. Environmental Protection Agency [1]: EDL values were determined from analysis of at
least 7 extracts from blank PUF disks spiked at the lowest point on the calibration curve for each
analyte. Each compound EDL was calculated based on the standard deviation of the average
mass determined multiplied by the appropriate Student t-value (Table S2). Average recoveries
for most analytes were adequate at 60-70%.
Calculation of Air Sampling Rates and Air Concentration Values. As stated in the Materials
and Methods, three isotopically-labeled chemicals, 13C6-hexachlorobenzene, diazinon (diethyld10), and d4-α-endosulfan, were spiked on each disk prior to deployment, and recoveries of these
chemicals along with their octanol-air partition coefficients KOA were used to estimate the
effective air sample volumes. Recoveries of the diazinon (diethyl-d10) were much lower than
expected from its estimated KOA value indicating this chemical was not stable over the sample
collection period. The average recovery of 13C6-hexachlorobenzene was 27%, but lower
recoveries were expected as this chemical is more volatile than most of the analytes. All samples
with very low recoveries were from the first sample period; average temperatures were 2 or 3
degrees higher during the first sampling period than the second period, and daytime temperatures
at some stations approached or exceeded 30 oC during the first period. However, these results
were still useful in calculating the air-side mass transfer rate values needed to determine effective
air sampling rates. The overall average recovery for d4-α-endosulfan was 80%. However, in
some samples recoveries were greater than 100%. Problems with poor chromatography for this
chemical may have contributed to inconsistent results. Results from 13C6-hexachlorobenzene
5
were found to be the most consistent, so resulting mass transfer rates derived from this chemical
were used in calculating air sampling rates for target analytes.
The air sampling rate derived from the depuration compound results, R (m3 day-1), is
calculated from the air-side mass transfer coefficient, ka (m day-1) and the PUF disk surface area,
A (m2).
R = ka A
(1)
The value of ka is dependent on the loss of depuration chemical, -ln(C/Co), the PUF disk volume
to surface area ratio, Dfilm (m); the dimensionless PUF/air partition coefficient, K’PUF-a’; and the
sampling time, t (days).
ka = -ln(C/Co) x Dfilm x K’PUF-a’/t
(2)
The relationship of log KPUF-a (PUF-Air partition coefficient) and log Koa (octanol-air partition
coefficient) has been established [2] as
Log KPUF-a = 0.6366 log Koa – 3.1774
(3)
The dimensionless K’PUF-a can be calculated from log KPUF-a using the density of the foam
material:
K’PUF-a [dimensionless]=(PUF density) x 10^( log KPUF-a)
(4)
Equations for the temperature dependence of Koa for specific chemicals have been determined [3,
4]. The temperature dependent Koa value for HCB may be determined from the following
equation where T = temperature (K):
log Koa = -2.39 + 2914/T
(5)
For example, the average air temperature for the entire sample period was used to calculate
sample-specific Koa values for HCB-13C6. If the average temperature was 12.3 oC, the HCB-13C6
recovery for a sample was C/Co = 0.37, and the sample collection time was 32 days:
6
13
log Koa value for HCB- C6 =7.82 using equation 5;
log KPUF-a = 1.80 using equation 3;
K’PUF-a [dimensionless] = 1.58x106 using equation 4;
ka = 251 (m/day) using equation 2; and
R = 8.5 (m3/day) using equation 1.
Since each chemical of interest has its own Koa value, an effective sample volume, Vair (m3) must
be calculated for each analyte.
Vair = (K'PUF-a) x (Vol. of PUF) x {1 - exp[-(time) x (ka)/(K'PUF-a)/(Dfilm)]}
(6)
The ka value derived from the depuration compound, HCB-13C6 was calculated for each sample.
K’PUF-a for the particular analyte was calculated as described above except that a temperatureadjusted Koa value for the analyte was utilized in equation 3. Since temperature depended Koa
values are not available for ß-endosulfan, the equation for α-endosulfan (log Koa = -5.9 +
4333/T) was used to calculate analyte-specific air volumes for this chemical.
7
Table S1. Detailed information for sites sampled. More than two sites are represented for some
Areas because tadpoles were not available from the same sites during both sampling periods.
“*” indicates site for air sampling. Universal Transverse Mercator (UTM) coordinates refer to
Zone 27, North American Datum 1927. Water body surface area and maximum depth refer to
water body selected for sampling; tadpoles were sometimes sampled in smaller adjacent,
detached water bodies. Surface area was derived from U.S. Geological Survey digitized
1:24,000-scale maps. Depth was derived by field measurements (R. Knapp, unpublished data).
Linear and upslope distances are from the edge of the San Joaquin Valley (see text).
Area
A
A
B
B
C
C
C
D
D
D
D
E
E
F
F
G
G
H
H
I
I
J
J
K
K
L
L
M
M
M
N
N
Final Site
No.
11684 *
11685
11474
11475 *
10594
12337 *
12338
10299 *
11281
10310
10311
11087 *
11089
12457 *
12461
12154
12155 *
10249
10525 *
21329
21559 *
20027 *
23058
20135
21522 *
20037
21317 *
21390 *
2310X
2030X
20062 *
21397
UTMEast
346316
346491
363722
363239
345221
345980
345670
370513
370794
372356
372140
373213
373505
349146
349069
369110
369332
362532
362273
352965
352562
361846
362156
376325
377404
355480
356237
366576
366680
366523
380257
382061
UTMNorth
4098263
4098247
4103540
4103102
4083175
4082685
4082590
4090485
4090172
4091251
4090703
4076951
4077097
4058420
4059154
4064790
4064509
4098611
4099102
4052710
4053011
4047219
4046811
4055173
4052640
4029177
4029744
4025941
4026573
4026636
4035963
4037072
Elevation
(m)
3241
3241
3260
3329
3234
3234
3188
3239
3291
3299
3343
3225
3232
2786
2796
3338
3304
3207
3202
3243
3186
3189
3239
3375
3365
3120
3241
3232
3177
3180
3262
3213
Surface
Area (ha)
0.05
0.06
0.07
0.06
2.07
0.15
0.37
0.57
0.07
3.05
1.62
0.21
0.08
0.09
0.06
0.17
0.24
10.12
0.68
0.39
0.18
6.44
0.03
0.81
0.23
1.08
0.15
0.29
0.50
--0.69
0.26
Max
Depth
(m)
0.50
0.30
1.00
0.40
7.30
2.00
7.75
2.70
0.25
1.75
3.40
1.50
0.50
0.75
1.25
0.50
3.00
14.50
5.80
1.50
1.50
6.40
0.10
2.00
0.50
2.00
1.50
1.40
1.50
--2.50
0.60
Linear
Distance
(km)
63.47
63.60
80.94
80.31
54.49
54.87
54.58
80.65
80.71
82.45
82.10
76.06
76.71
45.65
46.06
64.42
64.65
77.32
77.20
45.79
45.54
51.74
52.12
68.40
68.36
42.90
43.77
51.00
51.36
51.31
67.63
69.77
Upslope
Distance
(km)
96.13
96.11
116.33
116.47
85.47
86.59
86.78
125.62
126.62
128.43
128.58
124.46
123.96
111.52
111.08
117.14
116.74
108.99
108.74
62.48
61.98
182.58
182.53
187.33
184.90
59.57
60.34
163.16
162.58
162.78
176.30
177.57
Minimum
Maximum
Median
2786
3375
3237
0.03
10.12
0.24
0.10
14.50
1.50
42.90
82.45
64.01
59.57
187.33
116.94
8
Table S2. Target analytes and depuration chemicals included in passive air sample analysis
along with analytical parameters, estimated detection limits, and average spike recovery values.
Compound
Agricultural Pesticides
Chlorpyrifos
Chlorothalonil
Diazinon
α-endosulfan
β-endosulfan
Endosulfan sulfate
Fipronil
Malathion
Trifluralin
Banned Organochlorines
Aldrin
α-chlordane
γ-chlordane
4, 4’-DDD (1-chloro-4-[2,2-dichloro1-(4- chlorophenyl)ethyl]benzene)
4, 4’-DDE (1-chloro-4-[2,2-dichloro1-(4-chlorophenyl)ethenyl]benzene)
Dieldrin
α-hexachlorocyclohexane
γ-hexachlorocyclohexane
Heptachlor
Heptachlor Epoxide
Cis-nonachlor
Trans-nonachlor
Mirex
Polybrominated Diphenyl Ethers
BDE 47 (2,2',4,4' tetrabromodiphenyl ether)
BDE 100 (2,2',4,4',6 pentabromodiphenyl ether)
BDE 99 (2,2',4,4',5 pentabromodiphenyl ether)
BDE 154 (2,2',4,4',5',6 – hexabromo
diphenyl ether)
BDE 153 (2,2',4,4',5,5' – hexabromo
Mass of ions
monitored
(m/z)
Estimated
Detection
Limit (ng)
Average Spike
Recovery
(%)a
313, 315, 214
264,266,268
169, 303
406, 408, 412
406, 408, 404
386, 388, 384
384, 331, 400
157, 172
335, 305, 336
0.6
18
3.0
0.9
0.9
1.0
0.5
3.7
5.7
85
26
77
67
70
74
87
80
54
330, 237, 332
410, 408, 412
410, 412, 408
248, 250, 320
0.8
3.2
8.3
17
49
86
68
75
318, 320, 316, 281
4.3
60
346, 380, 237
255, 257, 71
255, 71, 257
266, 300, 232
318, 237, 388, 282
444, 442, 446
444, 442, 412
370, 404, 334, 439
1.0
1.8
0.7
0.6
1.1
0.7
1.8
1.0
58
50
50
67
53
72
67
78
161, 81, 79, 325
4.3
72
161, 484, 81, 79
1.9
70
161, 79, 484, 81
2.2
70
81, 644, 484, 564
2.4
62
81, 644, 484, 564
2.4
60
diphenyl ether)
Depuration Chemicals
Diazinon (diethyl-d10)
d4-α-endosulfan
13
C6-hexachlorobenzene
Internal Standards
2,2',3,4,4',5,6,6'-octachlorobiphenyl
δ-hexachlorocyclohexane
179, 303
410, 412, 408, 414
290, 292, 288, 294
430, 428, 394
255, 257, 71
a. n = 54 for depuration compound recoveries and n=7 for all other compounds
109
97
105
9
Table S3. Sediment semi-volatile organic compound estimated detection limits (EDLs).
Log
Koc
Sediment Estimated
Detection Limit
(ng/g dry weight)
Log
Koc
Sediment Estimated
Detection Limit (ng/g
dry weight)
Amide Pesticides
Thiocarbamate Pesticides
Alachlor
2.3
2.6
Acetochlor
2.3
11
Metolachlor
2.5
5.4
Propachlor
2.5
2.0
Organochlorines Pesticides and Metabolites
HCH (Hexachlorocyclohexane),
gamma
3.5
0.24
HCH, alpha
3.5
0.30
HCH, beta
3.5
0.46
HCH, delta
3.5
0.64
Methoxychlor
4.6
7.0
Heptachlor
4.7
2.8
Heptachlor epoxide
3.7
0.64
Hexachlorobenzene
3.5
0.0031
Endrin
4.0
2.6
Endrin aldehyde
4.0
0.21
Chlordane, trans
4.9
0.013
Chlordane, cis
4.9
0.28
Nonachlor, trans
5.2
0.037
Nonachlor, cis
5.2
0.041
Triallate
3.2
Triazine Herbicides and Metabolites
0.16
Cyanazine
Prometon
Atrazine
12
7.5
6.9
Chlordane, oxy
Dieldrin
Aldrin
o,p'-DDT
o,p'-DDD
(dichlorodiphenyldichloroethane)
o,p'-DDE
(dichlorodiphenyldichloroethylene)
p,p'-DDT
2.1
2.2
2.4
Simazine
2.2
Metribuzin
3.1
Miscellaneous Pesticides
Etridiazole
2.0
Dacthal
2.5
Trifluralin
4.0
Polycyclic Aromatic Hydrocarbons
20
0.40
9.4
0.027
0.024
3.9
4.0
5.0
5.4
0.39
2.8
0.67
3.5
Acenaphthylene
Acenaphthene
Fluorene
Anthracene
Phenanthrene
Pyrene
Fluoranthene
Chrysene +
Triphenylene
Benzo(a)anthracene
Retene
Benzo(k)fluoranthene
5.2
5.1
Benzo(a)pyrene
5.9
2.5
5.2
5.3
2.4
3.2
Benzo(b)fluoranthene
Benzo(e)pyrene
Indeno(1,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
5.9
5.9
7.0
9.0
6.4
6.4
6.4
16
6.8
1.3
p,p'-DDD
5.2
6.7
p,p'-DDE
5.2
6.7
Mirex
5.7
0.12
Organochlorine Sulfide Pesticides and
Metabolites
Endosulfan I
Endosulfan II
Endosulfan sulfate
Phosphorothioate
Pesticides
4.3
4.3
4.5
Methyl parathion
2.7
3.8
3.8
4.1
4.3
4.3
4.8
4.9
8.6
53
9.7
39
20
0.12
2.7
5.4
5.4
5.2
5.9
0.67
1.2
13
3.7
Polychlorinated Biphenyls
0.13
0.081
0.056
PCB 101
PCB 118
PCB 153
4.9
4.9
5.1
1.7
0.085
0.075
6.4
PCB 138
PCB 187
5.1
5.3
0.11
0.013
10
Malathion
Diazinon
Parathion
Ethion
Chlorpyrifos
1.5
3.1
3.3
4.1
3.8
20
3.3
19
3.6
0.41
PCB 183
Ave, Min, and Max EDLs
ave
max
min
5.3
0.032
5.5
53
0.0031
11
Table S4. Chemical concentrations and detection frequencies in sediment. Concentration values < estimated detection limit (EDL) have been
substituted with ½ EDL. “P25” and “P75” refer to 25th and 75th percentiles, respectively.
Dry-mass Basis (ng/g dry)
Chemical
Useable
N*
Detect
N**
Detect
Freq.***
Median
Min
Max
Carbon Basis (ng/g carbon)
P25
P75
Median
Min
Max
P25
P75
Period 1 (N=28):
Current-use
Pesticides
Chlorpyrifos
Dacthal
α-endosulfan
β-endosulfan
Endosulfan Sulfate
8
28
28
28
27
6
26
10
19
27
75.0%
92.9%
35.7%
67.9%
100.0%
0.107
0.117
0.017
0.180
1.758
0.043
0.003
0.002
0.001
0.074
3.478
5.379
4.412
7.095
31.194
0.082
0.048
0.008
0.011
0.790
0.706
0.323
0.256
0.558
5.312
1.730
1.929
0.426
2.124
26.147
0.285
0.018
0.059
0.057
2.112
12.438
28.659
15.775
25.369
111.548
0.852
0.922
0.168
0.330
13.321
5.751
4.113
1.957
5.647
61.521
Historic-use Pesticides
p,p'-DDE
Trans-chlordane
Cis-nonachlor
Trans-nonachlor
28
28
27
28
17
23
25
23
60.7%
82.1%
92.6%
82.1%
2.433
0.097
0.183
0.178
0.111
0.000
0.005
0.001
25.304
1.359
1.443
1.149
0.936
0.044
0.059
0.079
13.284
0.202
0.288
0.343
31.679
1.163
1.718
2.299
4.664
0.009
0.076
0.026
109.429
6.092
5.160
6.994
21.104
0.628
1.322
1.347
66.377
2.173
2.651
3.447
PCBs
PCB 138 (hexa)
PCB 153 (hexa)
PCB 183 (hepta)
PCB 187 (hepta)
28
27
26
26
27
18
16
22
96.4%
66.7%
61.5%
84.6%
0.029
0.047
0.011
0.049
0.002
0.001
0.001
0.000
0.428
0.285
0.122
0.241
0.013
0.019
0.004
0.016
0.113
0.127
0.029
0.091
0.502
0.684
0.144
0.394
0.075
0.118
0.028
0.041
1.570
4.437
2.670
3.234
0.265
0.357
0.102
0.287
1.071
1.152
0.265
0.675
PAHs
Benzo(b)fluoranthene
Fluoranthene
22
26
12
26
54.5%
100.0%
1.827
2.545
0.116
0.045
34.447
26.419
0.905
0.714
3.639
6.245
22.865
38.488
4.377
1.701
123.179
165.340
15.857
20.810
39.208
57.171
12
Dry-mass Basis (ng/g dry)
Chemical
Useable
N*
Detect
N**
Detect
Freq.***
Median
Carbon Basis (ng/g carbon)
Min
Max
P25
P75
Median
Min
Max
P25
P75
Period 2 (N=28):
Current-use
Pesticides
Chlorpyrifos
Dacthal
α-endosulfan
β-endosulfan
Endosulfan Sulfate
25
23
28
28
28
22
23
7
19
28
88.0%
100.0%
25.0%
67.9%
100.0%
0.101
0.220
0.013
0.164
1.104
0.011
0.015
0.002
0.001
0.031
2.276
3.187
3.094
4.742
31.551
0.038
0.069
0.006
0.005
0.266
0.227
0.591
0.126
0.827
5.043
1.372
2.109
0.297
1.198
15.183
0.499
0.440
0.060
0.079
2.212
10.717
19.085
17.974
26.136
188.929
0.999
1.228
0.156
0.285
7.810
3.587
5.029
0.795
6.057
33.129
Historic-use Pesticides
p,p'-DDE
Trans-chlordane
Cis-nonachlor
Trans-nonachlor
28
28
28
28
17
23
26
24
60.7%
82.1%
92.9%
85.7%
2.181
0.091
0.139
0.173
0.122
0.000
0.001
0.001
27.995
0.980
1.324
1.623
0.542
0.022
0.059
0.085
9.831
0.260
0.338
0.462
33.829
0.963
1.774
2.533
3.048
0.013
0.088
0.088
194.722
5.561
7.926
8.036
17.639
0.581
0.951
1.169
66.912
2.187
3.392
4.421
PCBs
PCB 138 (hexa)
PCB 153 (hexa)
PCB 183 (hepta)
PCB 187 (hepta)
28
28
28
28
27
24
18
27
96.4%
85.7%
64.3%
96.4%
0.048
0.067
0.009
0.033
0.002
0.001
0.001
0.000
0.504
1.005
0.143
0.367
0.007
0.026
0.004
0.015
0.114
0.194
0.030
0.107
0.515
1.028
0.146
0.520
0.052
0.104
0.015
0.053
3.020
4.037
0.673
1.730
0.270
0.578
0.078
0.333
1.080
1.864
0.271
0.872
PAHs
Benzo(b)fluoranthene
Fluoranthene
28
28
3
28
10.7%
100.0%
0.762
2.502
0.128
0.071
13.347
198.113
0.296
0.586
2.245
4.962
12.876
49.703
3.202
1.244
209.221
3105.462
7.130
15.984
22.574
85.944
* "Useable N" refers to samples not rejected because of high blank values.
** "Detect N" refers to samples not rejected because of high blank values and chemical was detected.
*** "Detect Freq." = Detect N/Useable N
13
Table S5. pH and electrical conductivity of water samples.
Period 1
Period 2
Mean ± SE
6.19 ± 0.07
6.37 ± 0.10
Range
5.37 - 6.94
5.01 - 7.36
28
27
Mean ± SE
8±1
15 ± 5
Range
1 - 27
3 - 127
28
28
pH
n
Conductivity (µS/cm)
n
14
Table S6. Chemical concentrations and detection frequencies in tadpoles. Concentration values < estimated detection limit (EDL) have been
substituted with ½ EDL. “P25” and “P75” refer to 25th and 75th percentiles, respectively.
Wet-mass Basis (ng/g wet)
Useable
N*
Dry-mass Basis (ng/g dry)
Lipid Basis (ng/g lipid)
Detect
N**
Detect
Freq.***
Median
Min
Max
P25
P75
Median
Min
Max
P25
P75
Median
Min
Max
P25
P75
24
21
19
27
21
20
13
25
87.5%
95.2%
68.4%
92.6%
0.048
0.091
0.033
0.051
0.010
0.004
0.007
0.003
0.082
0.313
0.128
0.202
0.041
0.065
0.009
0.030
0.060
0.151
0.051
0.079
0.716
1.125
0.386
0.692
0.146
0.065
0.051
0.036
1.351
4.726
1.896
2.969
0.437
0.737
0.138
0.458
0.806
1.643
0.880
0.964
22.244
36.885
12.008
19.290
2.224
4.096
2.616
1.251
156.11
156.11
61.339
135.75
12.229
24.015
4.436
10.627
29.266
61.211
21.210
39.216
27
26
96.3%
0.244
0.005
0.723
0.146
0.383
3.545
0.084
12.341
2.292
4.463
123.18
5.318
542.99
64.403
173.71
Historic-use Pesticides
p,p'-DDE
Trans-chlordane
Cis-nonachlor
Trans-nonachlor
27
13
27
27
14
13
16
20
51.9%
100.0%
59.3%
74.1%
0.238
0.014
0.008
0.014
0.116
0.001
0.003
0.001
0.974
0.025
0.031
0.044
0.127
0.011
0.003
0.001
0.520
0.018
0.015
0.025
3.850
0.150
0.102
0.188
0.813
0.033
0.019
0.004
10.767
0.410
0.390
0.542
1.715
0.131
0.051
0.020
5.960
0.210
0.173
0.270
131.30
5.818
3.311
4.863
26.069
1.476
0.596
0.274
1676.5
11.610
14.306
15.970
62.961
4.040
1.683
0.848
178.16
6.669
6.787
8.898
PCBs
PCB 153 (hexa)
PCB 183 (hepta)
PCB 187 (hepta)
12
26
27
8
4
19
66.7%
15.4%
70.4%
0.021
0.001
0.004
0.009
0.001
0.002
0.031
0.003
0.011
0.010
0.001
0.002
0.024
0.001
0.007
0.248
0.019
0.055
0.125
0.013
0.020
0.436
0.046
0.161
0.164
0.018
0.037
0.291
0.028
0.082
6.730
0.755
2.121
1.965
0.175
0.312
15.172
6.611
7.490
3.540
0.509
1.180
11.738
1.257
2.858
Chemical
Period 1 (N=27):
Current-use
Pesticides
Chlorpyrifos
Dacthal
α-endosulfan
β-endosulfan
Endosulfan
Sulfate
15
Wet-mass Basis (ng/g wet)
Dry-mass Basis (ng/g dry)
Lipid Basis (ng/g lipid)
Useable
N*
Detect
N**
Detect
Freq.***
Median
Min
Max
P25
P75
Median
Min
Max
P25
P75
Median
Min
Max
P25
P75
0
24
27
27
0
24
9
18
--100.0%
33.3%
66.7%
--0.152
0.008
0.056
--0.028
0.007
0.004
--0.728
0.282
0.248
--0.096
0.008
0.004
--0.283
0.092
0.095
--1.557
0.083
0.590
--0.243
0.064
0.031
--5.769
2.529
2.229
--0.935
0.073
0.035
--2.418
0.742
0.971
--19.895
1.505
7.280
--2.741
0.441
0.245
--68.426
36.137
28.488
--13.651
0.802
0.570
--32.674
13.701
13.996
27
26
96.3%
0.425
0.005
1.158
0.308
0.656
4.407
0.044
8.666
3.060
6.094
56.296
0.564
236.99
33.281
81.209
Historic-use Pesticides
p,p'-DDE
Trans-chlordane
Cis-nonachlor
Trans-nonachlor
27
27
27
27
18
25
20
20
66.7%
92.6%
74.1%
74.1%
0.601
0.038
0.043
0.052
0.118
0.001
0.003
0.001
1.909
0.071
0.106
0.114
0.132
0.030
0.003
0.001
0.863
0.056
0.056
0.081
4.750
0.336
0.392
0.454
1.068
0.005
0.025
0.005
16.393
0.546
0.886
1.018
1.432
0.295
0.054
0.011
9.369
0.491
0.589
0.758
54.242
4.518
4.507
5.247
8.775
0.085
0.304
0.056
272.59
12.795
16.689
22.252
20.283
2.924
0.859
0.172
127.49
7.713
8.150
12.225
PCBs
PCB 153 (hexa)
PCB 183 (hepta)
PCB 187 (hepta)
27
27
27
15
8
20
55.6%
29.6%
74.1%
0.028
0.001
0.010
0.009
0.001
0.001
0.096
0.025
0.041
0.010
0.001
0.002
0.046
0.010
0.016
0.242
0.015
0.102
0.078
0.011
0.013
1.030
0.265
0.446
0.094
0.012
0.028
0.404
0.085
0.140
3.705
0.209
1.198
0.528
0.077
0.102
9.475
2.569
4.496
1.155
0.162
0.450
6.232
1.184
2.367
Chemical
Period 2 (N=27):
Current-use
Pesticides
Chlorpyrifos
Dacthal
α-endosulfan
β-endosulfan
Endosulfan
Sulfate
* "Useable N" refers to samples not rejected because of high blank values.
** "Detect N" refers to samples not rejected because of high blank values and chemical was detected.
*** "Detect Freq." = Detect N/Useable N
16
Table S7. Principal components analysis (PCA) of chemical concentrations for pesticides and non-pesticides in sediment (carbon basis)
and tadpoles (dry-mass basis). Tadpole PCAs also include developmental stage as a variable. Concentration values < EDL were substituted
with ½ EDL. Sample sizes vary among PCAs because of missing values or low frequency of detection (<30%) for some chemicals (see
Materials and Methods). Bold (red) values indicate relatively high loadings for variable. Principal components analysis for non-pesticides in
tadpoles during Period 1 was not done because only PCB 187 had few missing values and detection frequency >30%.
PESTICIDES
Medium:
Sampling
Period:
Number
Chemicals:
Number
Samples:
Principal
Component:
Eigenvalue:
Chemical
loadings:
Chlorpyrifos
Dacthal
α-endosulfan
β-endosulfan
Endosulfan
Sulfate
p,p’-DDE
Transchlordane
Cisnonachlor
Transnonachlor
Tadpole
Stage
Sediment
Sediment
Tadpoles
Tadpoles
1
2
1
2
8
8
8
8
27
20
17
23
1
0.585
2
0.202
3
0.098
1
0.738
2
0.104
3
0.079
1
0.568
2
0.149
3
0.112
1
0.443
2
0.165
3
0.132
--0.319
0.352
0.388
---0.246
-0.448
-0.331
--0.600
0.016
-0.083
0.215
0.360
--0.365
0.911
-0.039
---0.088
-0.123
-0.338
---0.451
0.241
0.314
0.409
0.400
-0.011
-0.517
-0.256
-0.221
-0.142
0.234
0.010
-0.021
--0.133
0.306
0.282
--0.284
0.518
0.571
--0.297
0.168
-0.142
0.407
0.318
-0.127
0.235
-0.134
-0.662
0.381
0.338
-0.236
-0.308
-0.339
0.277
0.390
0.194
0.033
0.694
0.147
0.286
0.264
0.383
-0.304
-0.322
-0.473
-0.060
0.397
0.274
-0.073
0.403
0.028
0.121
---
---
---
0.456
-0.131
0.216
0.405
0.281
0.138
0.395
0.004
0.210
0.377
0.244
-0.126
0.440
-0.067
-0.015
0.187
0.636
0.389
0.336
0.093
0.646
0.394
0.257
0.133
0.439
-0.146
0.006
N/A
N/A
N/A
N/A
N/A
N/A
-0.171
-0.101
0.887
0.003
-0.293
0.767
17
NONPESTICIDES
Medium:
Sampling
Period:
Number
Chemicals:
Number
Samples:
Principal
Component:
Eigenvalue:
Chemical
loadings:
PCB 138
PCB 153
PCB 183
PCB 187
Fluoranthene
Tadpole
Stage
Sediment
Sediment
Tadpoles
Tadpoles
1
2
1
2
5
5
---
3
24
28
---
26
1
0.577
2
0.231
3
0.170
1
0.630
2
0.192
3
0.121
-----
-----
-----
1
0.659
2
0.248
3
0.059
0.055
0.551
0.572
0.573
0.194
0.720
0.259
-0.008
-0.095
-0.637
0.678
-0.163
-0.140
-0.006
0.703
0.392
0.485
0.524
0.539
0.216
0.279
-0.315
-0.107
-0.170
0.885
-0.844
0.319
0.034
0.129
0.409
-----------
-----------
-----------
--0.565
0.584
0.577
---
--0.017
0.025
0.104
---
--0.819
-0.318
-0.474
---
N/A
N/A
N/A
N/A
N/A
N/A
---
---
---
-0.085
0.994
0.044
18
Table S8. Spearman rank correlation test results for chemical concentrations (detects and
nondetects) and principal component 1 (PC_1) as a function of distance metrics (linear and
upslope distance) for sediment and tadpoles. PC_1 is derived from separate principal
components analyses for all pesticides and all PCB/PAHs (detects and nondetects). Values
shown for significant relationships are direction of relationship and p value. “ns” indicates not
significant. “----“ indicates chemical is not in dataset or detection frequency was <30% (Tables
S4 and S6).
Period 1
Sediment
Period 2
Tadpoles
Sediment
Tadpoles
Linear Upslope Linear Upslope Linear Upslope Linear Upslope
Pesticides
All Pesticides
(PC_1)
ns
Chlorpyrifos
ns
ns
ns
ns
+
0.037
0.037
ns
ns
ns
ns
----
----
Dacthal
ns
ns
ns
ns
ns
ns
ns
α-endosulfan
ns
ns
ns
ns
----
----
ns
ns
0.037
Β-endosulfan
ns
ns
ns
ns
ns
ns
ns
Endosulfan sulfate
ns
ns
ns
ns
ns
ns
0.012
ns
p.p’-DDE
ns
0.032
ns
ns
Trans-chlordane
ns
ns
ns
ns
ns
ns
Cis-nonachlor
ns
ns
ns
ns
ns
ns
Trans-nonachlor
ns
ns
ns
ns
ns
0.021
0.004
0.006
0.009
<0.001
ns
ns
ns
0.013
0.001
0.001
<0.001
----
0.001
ns
0.005
Non-Pesticides
All PCB/PAHs
(PC_1)
ns
ns
----
ns
ns
<0.001
ns
19
PCB 138
ns
ns
----
PCB 153
ns
ns
ns
---0.011
PCB 183
ns
ns
----
----
PCB 187
ns
ns
ns
ns
0.014
0.002
0.001
0.002
Benzofluoranthene
ns
ns
----
----
Fluoranthene
ns
ns
----
----
ns
----
---0.002
ns
ns
ns
ns
ns
ns
ns
0.023
----
----
----
----
ns
ns
----
----
20
Fig. S1. Relationships among linear distance, upslope distance, and elevation for sampled sites.
Two sites are represented from each area (n = 28; Fig. 1). A. Linear distance from the San
Joaquin Valley and elevation. B. Upslope distance from the Valley and elevation. C. Upslope
distance and linear distance.
21
Fig. S2. Loading scores for each chemical on principal component 1 (PC_1) for principal
components analysis for sediment (carbon basis) and tadpoles (dry-mass basis). Principal
components analysis for PCB/PAHs in tadpoles during Period 1 was not done because only PCB
187 was detected frequently. “Ev.” indicates eigenvalue for PC_1. “*” indicates chemical
omitted from analysis because it was not represented in dataset or many values were missing.
Samples sizes, specific values for principal components 1 through 3, and tadpole-stage scores are
provided in Table S7.
22
Fig. S3. Spatial interpolation for principal component 1 scores from principal components
analysis for pesticide concentrations in tadpoles during Period 2. “+” symbols indicate location
of site represented in PCA. Site locations and watershed boundaries correspond to those shown
in Fig. 1. Tick interval is 10 km. Spatial interpolation was done by kriging (Surfer 8; Golden
Software, Golden, CO).
23
Supporting Information References
1. U.S. Environmental Protection Agency. 2004. Test methods for evaluating solid waste,
physical/chemical methods, 3rd ed.; SW-864; U.S. Environmental Protection Agency:
Washington, DC. http://www.epa.gov/epaoswer/hazwaste/test/main.htm.
2. Shoeib M, Harner T 2002. Characterization and comparison of three passive air samplers for
persistent organic pollutants. Environ Sci Technol 36:4142-4151.
3. Shoeib M, Harner TM. 2002. Using measured octanol-air partition coefficients to explain
environmental partitioning of organochlorine pesticides. Environ Toxicol Chem 21:984990.
4. Harner T, Shoeib M. 2002. Measurements of octanol-air partition coefficients (Koa) for
polybrominated diphenyl ethers (PBDEs): predicting partitioning in the environment. J
Chem Eng Data 47:228-232.