Factors Affecting the Distribution of Perfluorinated Compounds in Sediments from Lake Shihwa, Korea
Jonathan E.
1United
1
Naile ,
Hoon
2
Yoo ,
Thomas M.
3
Jenkins ,
John W.
1
Washington
States Environmental Protection Agency, National Exposure Research Laboratory, Ecosystems Research Division
2National Reseach Council
3Senior Service America, Inc
ABSTRACT
Perfluorinated compounds (PFCs) are ubiquitously distributed in various environmental media including water, soil, sediment, and biota. PFCs have also been shown to biomagnify in both aquatic and terrestrial environments. Lake Shihwa is an artificial saltwater lake, located on the
west coast of Korea, which has been receiving industrial wastewater discharges from the Shihwa and Banweol Industrial complexes. Previous studies have reported elevated levels of PFCs in both water and biota samples. Sediment samples were collected from inside and outside the
Lake Shihwa industrial complex, where some of the highest water concentrations ever measured have been reported. Nine perfluorocarboxylate acids (PFCAs), five perfluorosulfonate acids (PFSAs) and six precursors (amides, acetates, and fluoro telomers) of perfluorooctane sulfonate
(PFOS) were surveyed using UPLC-MS-MS. In addition to determining sediment contamination profiles for PFCs and their precursor, other sediment physical characteristics were measured to understand the key factors affecting distribution dynamics of these halogenated chemicals in
this semi-closed artificial sea-lake environment. Interestingly, sampling locations where high waterborne or biota contamination had been previously reported coincided with highly contaminated sediment sites, supporting the existence of local point sources. Concentrations of PFCs
ranged from below the method detection limit (MDL=150 pg/g) to as high 246,805 pg/g dry weight. Two fluorotelomer alcohols (6:2FTS, 8:2 FTS) ranged from below the MDL (=100 pg/g each) to as great as 277 and 226 pg/g, respectively. In addition, two sulfonamides (sFOSA, FOSAA),
and two acetates (methylated, ethylated) were found at levels as high 32,172 pg/g (EtFOSAA) and 2,006 pg/g (MeFOSAA). The log-transformed distribution coefficient (LogKd), was found to be significantly associated with fluorinated carbon number (0.18 increment per C-F2 unit
addition). Overall this study provides useful field based distribution data for a wide variety of PFCs, which will be useful for future modeling efforts.
PFSAs/FOSAs Data in Lake Shihwa Sediments (pg/g dw)
Background
The C-F covalent bond is very strong and as a result PFCs are resistant to hydrolysis, photolysis,
metabolism, and biodegradation, but precursors such as fluorotelomer alcohols and
perfluorosulfonamides/acetates have been shown to degrade to more stable PFCs

Wide range of applications from surfactants and fire-fighting foams to pharmaceuticals

Globally ubiquitous in both remote and urban environments
Many unanswered questions still remain with respect to precursors, distribution and partitioning
throughout the environment
24
25
26
27
28
29
30
31
32
34
>LOQ (%)
<LOQ
<MDL
<MDL
<LOQ
181
<MDL
<MDL
<MDL
<MDL
<LOQ
10%
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
0%
1426
652
541
1338
1135
1379
1070
1886
480
439
100%
Fluorotelomer (FTS)
Perfluorooctanesulfonamides/acetates
PrePFOS (B)
Sample ID
Σ
Σ PFSA PrePFOS Ratio
(B)
(=A/B)
6:2FTS
8:2FTS
FOSA
FOSAA
MeFOSAA
EtFOSAA
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
0%
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
0%
< MDL
< MDL
< MDL
< MDL
< MDL
< MDL
< MDL
< MDL
< MDL
< MDL
0%
< LOQ
< MDL
< MDL
< LOQ
< LOQ
< MDL
< MDL
< LOQ
< MDL
< MDL
0%
444
< MDL
< MDL
< LOQ
< MDL
< LOQ
< LOQ
897
< MDL
< MDL
20%
674
< LOQ
< LOQ
410
432
276
183
1210
< LOQ
< MDL
70%
1536
652
541
1338
1316
1379
1070
2260
480
439
1118
102
98
410
432
276
183
2107
0
0
1.3
6.4
5.5
3.3
2.6
5.0
5.9
0.9
n.a.
n.a.
<MDL
140
<MDL
<LOQ
<MDL
<MDL
277
<MDL
<LOQ
<LOQ
20%
<MDL
<MDL
160
226
103
<LOQ
194
93
<MDL
<LOQ
50%
< MDL
1038
64
720
95
104
4331
110
82
2254
90%
< MDL
702
110
2932
231
399
568
475
< LOQ
1145
80%
< MDL
1797
< LOQ
2006
538
223
2778
489
771
1048
80%
122
7639
580
5892
1214
1435
32172
4833
536
9068
100%
742
10813
9700
71693
6195
4920
257875
38126
4454
25025
122
11177
753
11550
2079
2162
39849
5907
1389
13515
6.1
0.9
11.7
6.1
2.8
2.0
6.2
6.2
3.2
1.5
0
185
1348
0
1
88
113
1722
0
1
n.a.
1.6
0.6
n.a.
0.4
110
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<MDL
374
<MDL
<MDL
20%
Inland Sediment (Creeks in Industrial Complex, n=10)
Study Location
• The Shihwa and Banweol industrial complexes are located on the western coast of Korea
approximately 30 km south of Seoul
• Lake Shiwa is an artificial saltwater lake which receives industrial wastewater discharge from
both industrial complexes
• Historical contamination of organic compounds and metals in water and sediment
• Among the greatest water concentrations of PFOS and other PFCs ever reported
2
3
4
5
6
8
10
11
12
15
>LOQ (%)
<MDL
<MDL
667
419
<MDL
224
5123
872
<MDL
1008
60%
<MDL
<MDL
<MDL
<MDL
<MDL
<MDL
5010
<MDL
<MDL
2702
20%
742
9757
8803
70079
5916
4257
246805
36683
4454
20049
100%
<MDL
1056
229
1195
279
439
937
571
<MDL
1266
80%
Inland Sediment (Residential Complex, n=4)
17
19
20
21
>LOQ (%)
<MDL
<MDL
<MDL
<MDL
0%
<MDL
<MDL
<MDL
<MDL
0%
<MDL
185
1024
<MDL
50%
<MDL
<MDL
324
<MDL
25%
<MDL
<MDL
<MDL
<MDL
0%
<MDL
<MDL
<MDL
<MDL
0%
< MDL
< MDL
< LOQ
< MDL
0%
< MDL
< MDL
129
< MDL
25%
< MDL
< LOQ
186
< MDL
25%
88
113
1408
< MDL
75%
<MDL
<MDL
100
<MDL
<MDL
100
<MDL
<MDL
150
<MDL
<MDL
100
<MDL
<MDL
100
< MDL
< MDL
100
< MDL
< MDL
100
< MDL
< MDL
150
< MDL
< MDL
150
Procedural Blanks
• Home to a variety of terrestrial and aquatic wildlife species, e.g., migratory birds
• Sediment and water samples were collected from inland streams, Lake Shiwa, and Gyeonggi Bay
Sand
Tube
LOQ
<MDL
<MDL
100
C6
C7
C8
In Lake Sediments (n=10 sampling locations)
24
< LOQ
< MDL
273
25
< LOQ
< MDL
196
26
< LOQ
< MDL
152
27
< LOQ
< MDL
257
28
< LOQ
< MDL
< LOQ
29
< LOQ
< MDL
266
30
< LOQ
< MDL
134
31
< LOQ
< MDL
837
32
< MDL
< MDL
< LOQ
34
< LOQ
< MDL
< LOQ
> LOQ (%)
0%
0%
70%
Inland Sediments (Creeks in Industrial Complex, n=10)
2
149
< MDL
207
3
1044
453
3210
4
920
1511
2080
5
553
310
3301
6
182
< MDL
647
8
110
< MDL
290
10
1232
660
6624
11
308
< LOQ
1207
12
235
< LOQ
626
15
1262
330
8562
> LOQ (%)
100%
50%
100%
Inland Sediments (Creeks in Residential Complex, n=4)
17
< LOQ
< MDL
< LOQ
19
< MDL
< MDL
< LOQ
20
< LOQ
< MDL
237
21
< MDL
< MDL
< LOQ
> LOQ (%)
0%
0%
25%
Procedural Blanks
Sand
< MDL
< MDL
< LOQ
Tube
< MDL
< MDL
< MDL
LOQ
200
300
250
C9
C10
C11
C12
C13
C14
ΣPFCA
< LOQ
< LOQ
< MDL
< LOQ
< MDL
< LOQ
< LOQ
< LOQ
< MDL
< LOQ
0%
104
52
< LOQ
114
74
110
93
353
< LOQ
< LOQ
70%
297
134
177
462
364
337
188
554
62
< LOQ
90%
179
95
80
261
231
154
98
542
< LOQ
< MDL
80%
245
101
79
246
250
134
89
440
< LOQ
< LOQ
80%
81
< LOQ
< LOQ
73
< LOQ
< LOQ
< LOQ
295
< MDL
< MDL
30%
1179
578
486
1414
920
1002
602
3020
62
0
< MDL
1399
5271
2831
332
184
1378
324
207
2086
90%
< MDL
1856
1474
4169
359
137
1234
256
103
3793
90%
< LOQ
4844
5567
13911
1512
642
11964
1786
254
7797
90%
< LOQ
7264
705
4303
855
476
4313
871
349
8048
90%
< LOQ
7598
4114
5510
967
622
7093
574
445
14672
90%
< LOQ
9133
585
1701
359
228
2393
184
315
9997
90%
356
36801
22228
36591
5212
2688
36890
5511
2533
56548
< MDL
< MDL
< MDL
< MDL
0%
< MDL
< MDL
132
< LOQ
25%
< LOQ
< LOQ
215
< MDL
25%
< LOQ
< LOQ
712
< MDL
25%
< LOQ
< LOQ
643
< MDL
25%
< LOQ
< LOQ
590
< MDL
25%
0
0
2529
0
< MDL
< MDL
300
< MDL
< MDL
100
< MDL
< MDL
100
< MDL
< MDL
100
< MDL
< MDL
100
< MDL
< MDL
100
n.a.
n.a.
Sorption isotherms for PFSAs and PFCAs
Freundlich equation: Csed = Kf(Cw)n
6
Affects of Chain Length and Salinity on Sediment Distribution
Incheon City
0
4 km
Gyeonggi Bay
Kd vs Chain Length
1
30
34
32
31
3
5
8
9
25
24
27
33
26
28
7
10
11
23 22
12
13
14
15
16
4.0
4.0
y = 0.1772x + 0.8177
R² = 0.7618
Ansan City
4
2
6
Sea-dike
29
Shiheung City
Kd vs Salinity
17
19
18
20
21
Lake Shihwa
KOREA
Daebu
Is.
3.0
3.0
2.0
0.0
5
Hwaseong County
Discharge outlet (30)
Core sediment (33)
Duplicate (8, 12, 31)
6
7
8
F-Carbon Number
9
10
5
4
3
2
PFHxS
y = 0.9241x + 2.0143
R2 = 0.6798
1
PFOS
PFHxS
0
0.0
1.0
2.0
Log [PFCs-water] (ng/L)
2.0
y = -0.0141x + 2.0947
R² = 0.0159
0.0
5
6
7
8
Salinity(permille)
9
10
log Csed = nlog Cw + log Kf
5.0
4.0
3.0
3.0
Frndlch
PFHxA
PFHpA
2.0
PFOA
PFNA
1.0
PFDA
0.0
-1.0
1.0
1.0
PFOS
y = 1.0984x + 2.0435
R2 = 0.8195
Log [PFCs-sediment] (ng/kg)

Large scale production of PFOS and PFOA has been mostly phased out in North America but
significant manufacturing still persists in some Asian countries
Sample PFHxS
PFHpS
PFOS
PFDS
ID
(A)
In Lake Sediments (n=10 sampling locations)
Log (GM-Kd)

Perfluorosulfonic Acids (PFSAs)
Log [PFCs-sediment] (ng/kg)

PFCs have been produced and used in large quantities since the 1950s
Log (GM-Kd)

PFCA concentrations in Sediments (pg/g dry wt)
-1.0
0.0
1.0
Log [PFCs-water] (ng/L)
2.0
Cmpd
C6
C7
C8
C9
C10
n
log(Kf)
r2
0.934 1.931 0.768
1.056 1.832 0.259
1.047 1.762 0.594
1.504 1.964 0.523
1.292 2.618 0.284
Data
Signif.
Count
12
8
14
13
8
Level
0.01
ns
0.01
0.01
ns
References
Rostkowski et al. (2006) Perfluorinated compounds in streams of the Shiwa Industrial Zone and Lake Shiwa, South Korea.
Environmental Toxicology and Chemistry. (25) 9, pp 2374-2380
Higgins et al. (2006) Sorption of perfluorinated surfactants on sediments. Environmental Science and Technology. 40, pp 7251-7256
The log-transformed distribution coefficient Kd, was found to be significantly associated with fluorinated
carbon number on studied PFCs (0.18 increment per C-F2 unit addition), but no statistical associations between
Kd and salinity were found.
Yoo et al. (2009) Perfluoroalkyl acids in marine organisms from Lake Shiwa, Korea. Archives of Environmental Contamination and
Toxicology. 57, pp 552-560
Naile et al. (2010) Perfluorinated compounds in water, soil and biota from estuarine and costal areas of Korea. Environmental
Pollution. 158, pp 1237-1244