1
1
Comparing sorption behavior of pyrethroids between formulated and
2
natural sediments
3
Xinyi Cui†, Jay Gan†*
4
5
6
7
8
9
†
Department of Environmental Sciences, University of California, Riverside, CA
92521
Characterization of sediment properties
Total organic carbon (TOC) content in sediment was determined by removing
inorganic carbon with HCl digestion and then analyzing the digested sample by
10
combustion on an elemental analyzer (Flash EA1112 Combustion Nsitrogen/Carbon
11
Analyzer System, Thermo Finnigan, Woods Hole, MA, USA). The soot carbon content
12
was determined following the method of Gustafsson et al. [1]. Particle size distribution
13
was determined by using wet sieving in combination with centrifugation [2]. Sediment
14
pH and cation exchange capacity (CEC) were measured at the University of California
15
Agricultural and Natural Resources Analytical Laboratory in Davis, CA. Briefly, pH of
16
sediment was measured in the saturated paste extract by a pH meter. Barium is used to
17
quantitatively displace soil exchangeable cations for CEC measurement. A known
18
quantity of calcium is then exchanged for barium and excess calcium is measured. CEC
19
is calculated by the difference in the calcium added and left in the solution.
20
2
21
22
Characterization of supernatant properties
The dissolved organic carbon (DOC) content of the solutions was determined by
23
combustion of sample at 720°C on an Apollo 9000 total OC analyzer (Tekmar-Dohrmann,
24
Mason, OH, USA) after removing the inorganic carbon by acid digestion. The UV
25
absorbance of the supernatants at 254 nm was measured on a Shimadzu UV-1601
26
spectrophotometer (Shimadzu, Kyoto, Japan). The absorbance value (SUVA254), which
27
was previously shown to be related with aromatic carbon content of a DOC solution [3],
28
was determined by dividing the UV absorbance at 254 nm by the DOC concentration.
29
Meanwhile, the UV absorbance of the supernatants at 465 and 665 nm was also measured.
30
The ratio of absorbance at 465 and 665 nm (E4/E6) has been used as an empirical
31
indicator for aromaticity of humic materials [3].
32
3
33
34
Figure S1. Image of sediments used. Left: Little Harbor Beach sediment; Right:
35
formulated sediment A
4
36
Table S1. Selected properties of supernatant solutions in the present study
ABS254 (10-2)
DOC (mg/l)
E4/E6b
pH
a
(L/mg/m)
FSA
1.96
6.59
2.55
1.14
FSB
2.18
6.70
3.09
1.18
FSC
5.28
7.43
7.23
1.98
EMP37
1.94
5.45
2.66
1.18
EMP73
0.95
6.12
9.49
1.02
LHB
6.66
7.24
9.01
1.64
GCP
1.73
4.27
9.88
1.51
SC
1.60
6.76
1.23
1.04
37
a
38
254 nm by dissolved organic carbon (DOC) concentration of the supernatant.
39
b
ABS254 means specific absorbance at 254 nm calculated by dividing the absorbance at
E4/E6 is the ratio of absorbance at 465 and 665 nm.
5
40
Table S2 Distribution coefficient (Kd) values
Cyfluthrin
Cis-permethrin
Kd-SPME
Kd-app (104)
Kd-SPME
Ratioa
Kd-app (104)
4
Kd-SPME
Ratio
Kd-app (104)
4
(10 )
41
Trans-permethrin
Ratio
4
(10 )
(10 )
FSA
0.40±0.12
2.89±1.42
8.5±6.9
0.16±0.066
1.69±0.25
12.1±5.5
0.14±0.062
9.56±2.67
76.7±38.4
FSB
1.46±0.19
3.51±1.32
2.4±0.6
1.20±0.18
2.34±0.71
1.9±0.5
1.13±0.10
3.83±1.65
3.4±1.3
FSC
1.67±0.33
3.32±0.81
2.0±0.3
1.12±0.26
1.66±0.18
1.5±0.4
0.94±0.12
1.75±0.32
1.9±0.3
EMP37 0.34±0.0080 17.06±6.96
52.8±27.8
0.097±0.010 13.52±5.92 144.3±80.0 0.10±0.0083 34.69±4.28
334.1±44.8
EMP73 4.56±1.10
6.31±1.40
1.4±0.1
2.58±0.17
3.7±0.3
LHB
0.11±0.031
16.06±12.28 140.5±67.2 0.11±0.029
GCP
3.63±2.54
6.36±2.93
23.3±13.2
SC
20.41±1.70
4.01±1.47
2.0±0.7
a
Ratio of Kd-SPME over Kd-app.
4.28±1.13
1.7±0.5
2.46±0.28
8.98±1.11
11.07±5.23 97.7±23.6
0.12±0.034
18.03±12.15 142.1±59.3
0.39±0.23
9.64±3.52
30.9±17.4
0.51±0.15
18.33±0.60
31.4±5.6
11.87±1.64
2.23±0.58
1.9±0.3
1.03±0.23
3.97±1.50
4.0±2.0
6
42
Continuing with Table S2
Fenpropathrin
Esfenvalerate
Kd-SPME
Kd-app (104)
Kd-SPME
Ratioa
Kd-app (104)
4
44
Kd-SPME
Ratio
Kd-app (104)
4
(10 )
43
Deltamethrin
Ratio
4
(10 )
(10 )
FSA
0.089±0.030
0.30±0.076 3.6±1.2
0.26±0.14
12.93±5.33
57.3±27.8
0.22±0.11
4.61±1.57
26.6±15.8
FSB
0.39±0.041
0.60±0.17
1.5±0.3
2.03±0.20
8.56±5.40
4.1±2.2
1.89±0.22
6.20±3.83
3.2±1.7
FSC
0.25±0.083
0.26±0.058 1.1±0.2
2.48±0.35
8.15±2.24
3.3±0.6
2.46±0.19
5.07±0.89
2.1±0.2
EMP37 0.062±0.00092 2.84±0.64
45.6±10.7 0.13±0.016 72.86±24.66 587.2±260.6 0.091±0.0080 27.18±4.33 347.5±66.4
EMP73 0.68±0.099
1.14±0.23
1.7±0.3
4.47±0.82
LHB
0.12±0.034
2.53±0.97
21.1±3.3
GCP
3.56±2.03
3.70±0.78
12.4±5.4
SC
2.68±0.49
0.41±0.017 1.6±0.3
a
Ratio of Kd-SPME over Kd-app.
13.62±3.75
3.0±0.5
3.57±0.91
17.29±3.35 5.0±1.4
0.19±0.068 26.13±15.17 129.3±32.3
0.18±0.061
16.12±1.73 130.1±43.7
0.35±0.25
6.42±4.40
24.0±16.0
0.33±0.23
8.35±2.83
2.14±0.19
10.66±3.08
4.9±1.0
2.05±0.12
10.73±6.02 5.3±3.2
36.3±22.8
7
45
Table S3. The fraction of freely dissolved concentration (Cfree) in total aqueous phase concentration (CW) (Cfree/CW, %)
cisSediment
46
Bifenthrin
trans-
Fenpropathrin Cyhalothrin
Cyfluthrin
Permethrin
Permethrin
Esfenvalerate Deltamethrin
FSA
11.85
30.28
8.50
9.40
1.54
17.92
1.89
4.80
FSB
66.20
67.49
53.96
53.47
32.7
44.01
28.81
36.69
FSC
86.30
77.24
54.94
67.77
54.7
51.05
31.32
39.72
EMP37
1.31
2.27
0.95
0.82
0.30
2.26
0.20
0.32
EMP73
85.75
60.76
70.30
62.90
27.50
72.20
33.60
20.91
LHB
2.10
4.81
2.02
1.06
0.78
0.81
0.81
0.96
GCP
26.56
9.64
11.69
4.67
3.23
6.29
7.12
4.69
SC
51.02
65.97
32.40
54.40
28.71
55.24
24.04
20.87
FS a
54.78
58.34
39.14
43.55
29.64
37.66
20.67
27.07
Natural
33.35
28.69
23.47
24.77
12.10
27.36
13.15
9.55
a
FS and Natural are the average values for formulated and natural sediments.
8
47
48
REFERENCES
1. Gustafsson Ö, Haghseta F, Chan C, MacFarlane J, Gschwend PM. 1997.
49
Quantification of the dilute sedimentary soot phase: Implications for PAH speciation
50
and bioavailability. Environ Sci Technol 31:203-209.
51
2. Stemmer M, Gerzabeki MH, Kandeler E. 1998. Organic matter and enzyme activity
52
in particle-size fractions of soils obtained after low-energy sonication. Soil Biol
53
Biochem 30:9-17.
54
3. Korshin GV, Li CW, and Benjamin MM. 1997. Monitoring the properties of natural
55
organic matter through UV spectroscopy: Aconsistent theory. Water Res 31:1787-
56
1795.