Factors Affecting the Distribution of Perfluorinated Compounds in Sediments from Lake Shihwa, Korea

Jonathan E. Naile1, Hoon Yoo2, Thomas M. Jenkins3, John W. Washington1

1United States Environmental Protection Agency, National Exposure Research Laboratory, Ecosystems Research Division2National Reseach Council

3Senior Service America, Inc

PFCs have been produced and used in large quantities since the 1950s 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 Large scale production of PFOS and PFOA has been mostly phased out in North America but

significant manufacturing still persists in some Asian countries Many unanswered questions still remain with respect to precursors, distribution and partitioning

throughout the environment

Background

Study Location

PFSAs/FOSAs Data in Lake Shihwa Sediments (pg/g dw)

References

ABSTRACT

PFCA concentrations in Sediments (pg/g dry wt)

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.

Sample ID C6 C7 C8 C9 C10 C11 C12 C13 C14 ΣPFCAIn Lake Sediments (n=10 sampling locations)

24 < LOQ < MDL 273 < LOQ 104 297 179 245 81 117925 < LOQ < MDL 196 < LOQ 52 134 95 101 < LOQ 57826 < LOQ < MDL 152 < MDL < LOQ 177 80 79 < LOQ 48627 < LOQ < MDL 257 < LOQ 114 462 261 246 73 141428 < LOQ < MDL < LOQ < MDL 74 364 231 250 < LOQ 92029 < LOQ < MDL 266 < LOQ 110 337 154 134 < LOQ 100230 < LOQ < MDL 134 < LOQ 93 188 98 89 < LOQ 60231 < LOQ < MDL 837 < LOQ 353 554 542 440 295 302032 < MDL < MDL < LOQ < MDL < LOQ 62 < LOQ < LOQ < MDL 6234 < LOQ < MDL < LOQ < LOQ < LOQ < LOQ < MDL < LOQ < MDL 0

> LOQ (%) 0% 0% 70% 0% 70% 90% 80% 80% 30% Inland Sediments (Creeks in Industrial Complex, n=10)

2 149 < MDL 207 < MDL < MDL < LOQ < LOQ < LOQ < LOQ 3563 1044 453 3210 1399 1856 4844 7264 7598 9133 368014 920 1511 2080 5271 1474 5567 705 4114 585 222285 553 310 3301 2831 4169 13911 4303 5510 1701 365916 182 < MDL 647 332 359 1512 855 967 359 52128 110 < MDL 290 184 137 642 476 622 228 2688

10 1232 660 6624 1378 1234 11964 4313 7093 2393 3689011 308 < LOQ 1207 324 256 1786 871 574 184 551112 235 < LOQ 626 207 103 254 349 445 315 253315 1262 330 8562 2086 3793 7797 8048 14672 9997 56548

> LOQ (%) 100% 50% 100% 90% 90% 90% 90% 90% 90% Inland Sediments (Creeks in Residential Complex, n=4)

17 < LOQ < MDL < LOQ < MDL < MDL < LOQ < LOQ < LOQ < LOQ 019 < MDL < MDL < LOQ < MDL < MDL < LOQ < LOQ < LOQ < LOQ 020 < LOQ < MDL 237 < MDL 132 215 712 643 590 252921 < MDL < MDL < LOQ < MDL < LOQ < MDL < MDL < MDL < MDL 0

> LOQ (%) 0% 0% 25% 0% 25% 25% 25% 25% 25% Procedural Blanks

Sand < MDL < MDL < LOQ < MDL < MDL < MDL < MDL < MDL < MDL Tube < MDL < MDL < MDL < MDL < MDL < MDL < MDL < MDL < MDL LOQ 200 300 250 300 100 100 100 100 100

Perfluorosulfonic Acids (PFSAs) Fluorotelomer (FTS)

Perfluorooctanesulfonamides/acetates PrePFOS (B)

Sample PFHxS PFHpS PFOS PFDS 6:2FTS 8:2FTS FOSA FOSAA Me- Et- Σ PFSAΣ

PrePFOS RatioID (A) FOSAA FOSAA (B) (=A/B)

In Lake Sediments (n=10 sampling locations)

24 <LOQ <MDL 1426 110 <MDL <MDL < MDL < LOQ 444 674 1536 1118 1.325 <MDL <MDL 652 <LOQ <MDL <MDL < MDL < MDL < MDL < LOQ 652 102 6.426 <MDL <MDL 541 <LOQ <MDL <MDL < MDL < MDL < MDL < LOQ 541 98 5.527 <LOQ <MDL 1338 <LOQ <MDL <MDL < MDL < LOQ < LOQ 410 1338 410 3.328 181 <MDL 1135 <LOQ <MDL <MDL < MDL < LOQ < MDL 432 1316 432 2.629 <MDL <MDL 1379 <LOQ <MDL <MDL < MDL < MDL < LOQ 276 1379 276 5.030 <MDL <MDL 1070 <MDL <MDL <MDL < MDL < MDL < LOQ 183 1070 183 5.931 <MDL <MDL 1886 374 <MDL <MDL < MDL < LOQ 897 1210 2260 2107 0.932 <MDL <MDL 480 <MDL <MDL <MDL < MDL < MDL < MDL < LOQ 480 0 n.a.34 <LOQ <MDL 439 <MDL <MDL <MDL < MDL < MDL < MDL < MDL 439 0 n.a.

>LOQ (%) 10% 0% 100% 20% 0% 0% 0% 0% 20% 70% Inland Sediment (Creeks in Industrial Complex, n=10)

2 <MDL <MDL 742 <MDL <MDL <MDL < MDL < MDL < MDL 122 742 122 6.13 <MDL <MDL 9757 1056 140 <MDL 1038 702 1797 7639 10813 11177 0.94 667 <MDL 8803 229 <MDL 160 64 110 < LOQ 580 9700 753 11.75 419 <MDL 70079 1195 <LOQ 226 720 2932 2006 5892 71693 11550 6.16 <MDL <MDL 5916 279 <MDL 103 95 231 538 1214 6195 2079 2.88 224 <MDL 4257 439 <MDL <LOQ 104 399 223 1435 4920 2162 2.0

10 5123 5010 246805 937 277 194 4331 568 2778 32172 257875 39849 6.211 872 <MDL 36683 571 <MDL 93 110 475 489 4833 38126 5907 6.212 <MDL <MDL 4454 <MDL <LOQ <MDL 82 < LOQ 771 536 4454 1389 3.215 1008 2702 20049 1266 <LOQ <LOQ 2254 1145 1048 9068 25025 13515 1.5

>LOQ (%) 60% 20% 100% 80% 20% 50% 90% 80% 80% 100% Inland Sediment (Residential Complex, n=4)

17 <MDL <MDL <MDL <MDL <MDL <MDL < MDL < MDL < MDL 88 0 88 n.a.19 <MDL <MDL 185 <MDL <MDL <MDL < MDL < MDL < LOQ 113 185 113 1.620 <MDL <MDL 1024 324 <MDL <MDL < LOQ 129 186 1408 1348 1722 0.621 <MDL <MDL <MDL <MDL <MDL <MDL < MDL < MDL < MDL < MDL 0 0 n.a.

>LOQ (%) 0% 0% 50% 25% 0% 0% 0% 25% 25% 75% 1 1 0.4Procedural Blanks

Sand <MDL <MDL <MDL <MDL <MDL <MDL < MDL < MDL < MDL < MDL n.a.Tube <MDL <MDL <MDL <MDL <MDL <MDL < MDL < MDL < MDL < MDL n.a.LOQ 100 100 100 150 100 100 100 100 150 150

5 6 7 8 9 100.0

1.0

2.0

3.0

4.0

f(x) = 0.177215623799824 x + 0.817671794614007R² = 0.761795893057306

Kd vs Chain Length

F-Carbon Number

Log

(GM

-Kd)

• 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

• 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

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

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

D is c h a r g e o u t l e t (3 0 )C o re s e d im e n t (3 3 )D u p li c a te ( 8 , 1 2 , 3 1 )

Sea-d ike

G yeongg i B ay

L ake Sh ihw a

Shiheung C ity

Incheon C ity

A nsan C ity

H w aseong C oun ty

0 4 km

D aebuIs.

2 22 3

2 42 5

2 6

2 7

2 82 9

3 0

3 13 2

3 3

3 41

23

45

67

89

1 011

1 21 3

1 4

1 51 6

1 7

1 81 9

2 02 1

K O R E A

-1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50

1

2

3

4

5

6

f(x) = 0.92408110497093 x + 2.01426934947268R² = 0.679763345727682

f(x) = 1.09841155279014 x + 2.04350692100413R² = 0.819479964484591

PFOSLinear (PFOS)PFHxS

Log [PFCs-water] (ng/L)

Log

[PFC

s-se

dim

ent]

(ng/

kg)

-1.0 0.0 1.0 2.00.0

1.0

2.0

3.0

4.0

5.0

PFHxA

PFHpA

PFOA

PFNA

PFDA

Log [PFCs-water] (ng/L)

Log

[PFC

s-se

dim

ent]

(ng/

kg)

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.

5 6 7 8 9 100.0

1.0

2.0

3.0

4.0

f(x) = NaN x + NaNR² = 0 Kd vs Salinity

Salinity(permille)

Log

(GM

-Kd)

Frndlch Data Signif.

Cmpd n log(Kf) r2 Count LevelC6 0.934 1.931 0.768 12 0.01C7 1.056 1.832 0.259 8 nsC8 1.047 1.762 0.594 14 0.01C9 1.504 1.964 0.523 13 0.01

C10 1.292 2.618 0.284 8 ns

Sorption isotherms for PFSAs and PFCAs

Freundlich equation: Csed = Kf(Cw)n

log Csed = nlog Cw + log KfAffects of Chain Length and Salinity on Sediment Distribution