Supplemental Data
MANUSCRIPT TITLE:
Assessing bioavailability of DDT and metabolites in marine
sediments using solid phase microextraction with performance
reference compounds
AUTHORS:
Lian-Jun Bao, Fang Jia, J. Crago, Eddy Y. Zeng, D. Schlenk, and Jay
Gan
ADDRESS:
Department of Environmental Science, University of California,
Riverside; State Key Laboratory of Organic Geochemistry,
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences,
Guangzhou 510640, China
FIGURES:
3
TABLES:
5
NO. OF PAGES:
10
1
Table S1. Organic carbon (OC, %) content in sediments.
Sediment
OC (%)
Sediment
OC (%)
NBa
0.68
PV8Cc
3.08
NB + 2% Sand
0.68
PV8C + 0.5% Sand
3.03
NB + 5% Sand
0.60
PV8C + 2% Sand
3.51
NB + 0.5% ACb
1.06
PV8C + 5% Sand
3.06
NB + 2% AC
2.31
PV8C + 0.5% AC
3.42
NB + 5% AC
4.95
PV8C + 2% AC
4.95
NFd
0.27
PV8C + 5% AC
6.87
a
Sediment was collected from Newport Bay, CA;
b
AC = activated carbon; c Sediments were
collected from Palos Verdes Shelf Superfund site, CA;
Fields in Port Gamble, WA
2
d
Sediment was obtained from New
Table S2. Preloaded amount (ng) of PRCs on the 35-µm disposable polydimethylsiloxane
(PDMS) fiber in the test and different treatments (Table S1) for isotropy validation. The data are
shown as mean ± SD, and relative standard deviation (RSD).
PRCs
Test
M
NB
RSD
(n =9)
M
NB + 2% sand
RSD
(n = 5)
M
RSD
(n = 5)
NB + 5% sand
M
RSD
(n = 5)
13
18 ± 0.43
2.4
14 ± 0.60 4.2
13 ± 0.22 1.7
13 ± 0.12 0.9
p,p'-DDE-d8
23 ± 0.51
2.3
15 ± 0.84 5.8
13 ± 0.22 1.6
13 ± 0.12 0.9
13
11 ± 0.27
2.4
11 ± 0.5
10 ± 0.23 2.2
12 ± 0.16 1.5
p,p'-DDD-d8
7.1 ± 0.25
3.6
12 ± 0.55 4.7
9 ± 0.17
9.6 ± 0.17 1.7
o,p'-DDT-d8
12 ± 0.26
2.9
p,p'-DDT-d8
9.1 ± 0.28
3.1
PRCs
NB + 0.5% AC
C-o,p'-DDE
C-o,p'-DDD
M
RSD
(n =5)
4.5
NB + 2% AC
M
RSD
(n = 5)
1.8
NB + 5% AC
M
RSD
(n = 5)
13
12 ± 0.26
2.1
16 ± 0.41 2.6
19 ± 0.61 3.3
p,p'-DDE-d8
13 ± 0.26
2.1
16 ± 0.40 2.5
18 ± 0.82 4.5
13
11 ± 0.28
2.5
13 ± 0.62 4.9
14 ± 0.73 5.1
p,p'-DDD-d8
11 ± 0.28
2.4
13 ± 0.29 2.3
16 ± 0.84 5.2
C-o,p'-DDE
C-o,p'-DDD
NF
M
RSD
(n = 5)
o,p'-DDT-d8
12 ± 0.7
5.8
p,p'-DDD-d8
7.8 ± 0.9
11
3
Table S3. Fitted parameters from a regression absorption equation, n = ne*(1-exp (-kabst)), of dichlorodiphenyltrichloroethane (DDT)
and its metabolites and another regression desorption equation, q = q0*(exp(-kdest)), of corresponding PRCs (performance reference
compounds) on 35-µm disposable polydimethylsiloxane (PDMS) fiber in NB sediments amended without and with sand or activated
carbon (AC) and NF sediment in the mixing condition.
Compound
r2
kabs
p
PRC
r2
kdes
p
NBa
o,p'-DDE
0.99
0.043 ± 0.0024
< 0.0001
13
0.99
0.046 ± 0.002
< 0.0001
p,p'-DDE
0.99
0.036 ± 0.0016
< 0.0001
p,p'-DDE-d8
0.99
0.041 ± 0.002
< 0.0001
o,p'-DDD
0.97
0.24 ± 0.027
< 0.0001
13
0.99
0.18 ± 0.011
< 0.0001
p,p'-DDD
0.92
0.30 ±0.067
0.0039
p,p'-DDD-d8
0.99
0.20 ± 0.005
< 0.0001
C-o,p'-DDE
C-o,p'-DDD
NB + 0.5% AC
o,p'-DDE
0.98
0.043 ± 0.005
< 0.0001
13
0.99
0.049 ± 0.003
< 0.0001
p,p'-DDE
0.98
0.037 ± 0.004
< 0.0001
p,p'-DDE-d8
0.99
0.042 ± 0.002
< 0.0001
o,p'-DDD
0.94
0.19 ± 0.032
0.0004
13
0.99
0.25 ± 0.009
< 0.0001
p,p'-DDD
0.95
0.29 ± 0.051
0.0005
p,p'-DDD-d8
0.99
0.22 ± 0.013
< 0.0001
C-o,p'-DDE
C-o,p'-DDD
NB + 2% AC
o,p'-DDE
0.99
0.074 ± 0.004
< 0.0001
13
0.99
0.056 ± 0.002
< 0.0001
p,p'-DDE
0.99
0.066 ± 0.004
< 0.0001
p,p'-DDE-d8
0.99
0.051 ± 0.002
< 0.0001
o,p'-DDD
0.98
0.37 ± 0.045
< 0.0001
13
0.99
0.29 ± 0.006
< 0.0001
p,p'-DDD
0.94
0.39 ± 0.082
0.0014
p,p'-DDD-d8
0.99
0.24 ± 0.019
< 0.0001
0.99
0.063 ± 0.002
< 0.0001
C-o,p'-DDE
C-o,p'-DDD
NB + 5% AC
o,p'-DDE
13
C-o,p'-DDE
4
p,p'-DDE
p,p'-DDE-d8
0.99
0.055 ± 0.01
< 0.0001
o,p'-DDD
13
0.97
0.32 ± 0.005
< 0.0001
p,p'-DDD
p,p'-DDD-d8
0.99
0.29 ± 0.021
< 0.0001
C-o,p'-DDD
NB + 2% Sand
o,p'-DDE
0.99
0.063 ± 0.002
< 0.0001
13
0.99
0.051 ± 0.003
< 0.0001
p,p'-DDE
0.99
0.049 ± 0.001
< 0.0001
p,p'-DDE-d8
0.99
0.0498 ± 0.001
< 0.0001
o,p'-DDD
0.99
0.34 ± 0.032
< 0.0001
13
0.99
0.33 ± 0.007
< 0.0001
p,p'-DDD
0.98
0.45 ± 0.058
< 0.0001
p,p'-DDD-d8
0.98
0.29 ± 0.027
< 0.0001
C-o,p'-DDE
C-o,p'-DDD
NB + 5% Sand
o,p'-DDE
0.99
0.066 ± 0.003
< 0.0001
13
0.99
0.063 ± 0.002
< 0.0001
p,p'-DDE
0.99
0.051 ± 0.002
< 0.0001
p,p'-DDE-d8
0.99
0.055 ± 0.001
< 0.0001
o,p'-DDD
0.99
0.32 ± 0.024
< 0.0001
13
0.99
0.32 ± 0.005
< 0.0001
p,p'-DDD
0.99
0.54 ± 0.061
< 0.0001
p,p'-DDD-d8
0.99
0.29 ± 0.02
< 0.0001
C-o,p'-DDE
C-o,p'-DDD
NFb
o,p'-DDT
0.99
0.034 ± 0.001
< 0.0001
o,p'-DDT-d8
0.98
0.036 ± 0.003
< 0.0001
p,p'-DDT
0.99
0.048 ± 0.003
< 0.0001
p,p'-DDT-d8
0.99
0.055 ± 0.004
< 0.0001
a
Sediment was collected from Newport Bay, CA and spiked with DDTs; b Sediment was collected from New Fields in Port Gamble,
WA and spiked with o,p'-DDT and p,p'-DDT.
5
Table S4. Percentage of depletion for PRCs from 35-µm PDMS fiber into PV8C sediment amended without and with 0.5, 2 and 5% sand or
activated carbon (AC).
PV8C
PV8C + 0.5% Sand
PV8C + 2% Sand
PV8C + 5% Sand
PV8C + 0.5% AC
PV8C + 2% AC
PV8C + 5% AC
13
20 ± 1.8
19 ± 2.9
21 ± 1.4
17 ± 7.5
18 ± 2.1
25 ± 0.7
18 ± 8.4
p,p'-DDE-d8
17 ± 2.1
17 ± 2.6
19 ± 1.4
16 ± 6.3
16 ± 2.5
22 ± 0.8
16 ± 7.3
13
82 ± 2.0
81 ± 4.4
85 ± 0.8
58 ± 23
81 ± 1.7
85 ± 1.0
72 ± 25
p,p'-DDD-d8
75 ± 1.4
74 ± 2.5
76 ± 1.1
57 ± 17
73 ± 0.6
78 ± 1.3
68 ± 18
o,p'-DDT-d8
30 ± 12
32 ± 4.5
36 ± 4.1
22 ± 8.7
34 ± 3.3
22 ± 22
23 ± 14
p,p'-DDT-d8
42 ± 15
45 ± 5.7
50 ± 5.2
31 ± 12
48 ± 5.5
30 ± 29
33 ± 20
C-o,p'-DDE
C-o,p'-DDD
6
Table S5. Spiked concentrations of DDTs (ng/g) in different sediment amended with and without activated carbon (AC) and sand. The data are
shown as mean ± SD
NBa
NB + 0.5% AC
NB + 2% AC
NB + 5% AC
NB + 2% Sand
NB + 5% Sand
PV8Cb
NFc
o,p'-DDE
119 ± 48
136 ± 18
105 ± 3
105 ± 13
135 ± 20
120 ± 0.4
3488 ± 149
p,p'-DDE
130 ± 53
148 ± 19
117 ± 4.7
117 ± 16
146 ± 21
129 ± 1.2
19393 ± 1374
o,p'-DDD
154 ± 64
170 ± 21
139 ± 4.4
146 ± 21
213 ± 46
165 ± 3.4
2664 ± 869
p,p'-DDD
123 ± 54
132 ± 17
116 ± 5.7
129 ± 20
137 ± 18
119 ± 2.6
16399 ± 9569
o,p'-DDT
15 ± 6.9
8.0 ± 1.2
29 ± 1.4
79 ± 11
5.1 ± 1.1
8.6 ±1.6
256 ± 293
1074 ± 98
p,p'-DDT
10 ± 6.7
5.4 ± 0.9
15 ± 0.7
45 ± 9.5
2.7 ± 0.3
3.3 ± 0.3
1615 ± 226
958 ± 112
a
Sediment was collected from Newport Bay, CA; b Sediments were acquired from Palos Verdes Shelf Superfund site, CA; c Sediment was obtained
from New Fields in Port Gamble, WA.
7
120
120
(a)
(b)
100
80
80
60
60
100*(1-q/q0)
100
40
40
13
C-o,p'-DDE
13
C-o,p'-DDD
p,p'-DDE-d8
20
0
13
50
9
120
100
150
200
250
300
100*(1-q/q0)
p,p'-DDD-d8
0 9
30
60
120
(c)
100
90
120
150
(d)
100
80
80
60
60
40
40
13
13
C-o,p'-DDE
13
C-o,p'-DDD
p,p'-DDE-d8
20
0
0 9
30
60
90
120
C-o,p'-DDE
C-o,p'-DDD
p,p'-DDE-d8
20
13
0
p,p'-DDD-d8
120
100*(1-q/q0)
13
0
p,p'-DDD-d8
0
C-o,p'-DDE
C-o,p'-DDD
p,p'-DDE-d8
20
150
p,p'-DDD-d8
0
9
20
40
120
(e)
100
100
80
80
60
60
40
60
80
100
(f)
40
13
13
C-o,p'-DDE
13
C-o,p'-DDD
p,p'-DDE-d8
20
0
30
60
90
120
13
0
p,p'-DDD-d8
0 9
C-o,p'-DDE
C-o,p'-DDD
p,p'-DDE-d8
20
150
Exposed time (h)
p,p'-DDD-d8
0 9
30
60
90
120
150
Exposed time (h)
Figure S1. Depletion of PRC (13C-o,p'-DDE, 13C-o,p'-DDD, p,p'-DDE-d8 and p,p'-DDD-d8) from
PDMS fiber in the different sediments. (a) NB sediment; (b) NB amended with
0.5% activated carbon (AC); (c) NB amended with 2% AC; (d) NB amended
with 5% AC; (e) NB amended with 2% sand; (f) NB amended with 5% sand.
q0 is the initial amount of PRC on the fiber; q is the amount of PRC remaining
on the fiber at time t.
8
120
100*(1-q/q0)
100
80
60
40
20
0
o,p'-DDT-d8
p,p'-DDT-d8
-20
0
9
50
100
150
200
250
Exposed time (h)
Figure S2. Depletion of PRC (o,p'-DDT-d8 and p,p'-DDT-d8) from PDMS fiber in the NF
sediment. (q0 is the initial amount of PRC on the fiber; q is the amount of PRC
remaining on the fiber at time t)
9
6.5
o,p'-DDE
p,p'-DDE
o,p'-DDD
o,p'-DDT
p,p'-DDD
p,p'-DDT
log (CPDMS/Cw)
6.0
5.5
5.0
4.5
0
5
10
15
20
25
30
Extraction time (d)
Figure S3. Sorption kinetics of DDTs on the 35-µm disposable polydimethylsiloxane (PDMS)
fiber expressed as Cpe/Cw versus time (day), where Cpe and Cw are the
concentrations of an analyte on the PDMS fiber and seawater with salinity of
35‰, respectively.
10