1. Factors Affecting the Distribution of Perfluorinated Compounds in Sediments from Lake Shihwa, Korea Jonathan E. Naile 1, Hoon Yoo 2, Thomas M. Jenkins 3, John W. Washington 1 1 United States Environmental Protection Agency, National Exposure Research Laboratory, Ecosystems Research Division 2 National Reseach Council 3 Senior 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 (LogK d ), was found to be significantly associated with fluorinated carbon number (0.18 increment per C-F 2 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 IDC6C7C8C9C10C11C12C13C14ΣPFCA In Lake Sediments (n=10 sampling locations) 24< LOQ< MDL273< LOQ104297179245811179 25< LOQ< MDL196< LOQ5213495101< LOQ578 26< LOQ< MDL152< MDL< LOQ1778079< LOQ486 27< LOQ< MDL257< LOQ114462261246731414 28< LOQ< MDL< LOQ< MDL74364231250< LOQ920 29< LOQ< MDL266< LOQ110337154134< LOQ1002 30< LOQ< MDL134< LOQ931889889< LOQ602 31< LOQ< MDL837< LOQ3535545424402953020 32< MDL < LOQ< MDL< LOQ62< LOQ < MDL62 34< LOQ< MDL< LOQ < MDL< LOQ< MDL0 > LOQ (%)0% 70%0%70%90%80% 30% Inland Sediments (Creeks in Industrial Complex, n=10) 2149< MDL207< MDL < LOQ 356 31044453321013991856484472647598913336801 492015112080527114745567705411458522228 55533103301283141691391143035510170136591 6182< MDL64733235915128559673595212 8110< MDL2901841376424766222282688 1012326606624137812341196443137093239336890 11308< LOQ120732425617868715741845511 12235< LOQ6262071032543494453152533 1512623308562208637937797804814672999756548 > LOQ (%)100%50%100%90% Inland Sediments (Creeks in Residential Complex, n=4) 17< LOQ< MDL< LOQ< MDL < LOQ 0 19< MDL < LOQ< MDL < LOQ 0 20< LOQ< MDL237< MDL1322157126435902529 21< MDL < LOQ< MDL< LOQ< MDL 0 > LOQ (%)0% 25%0%25% Procedural Blanks Sand< MDL < LOQ< MDL Tube< MDL LOQ200300250300100 Perfluorosulfonic Acids (PFSAs)Fluorotelomer (FTS) Perfluorooctanesulfonamides/acetates PrePFOS (B) SamplePFHxSPFHpSPFOSPFDS6:2FTS8:2FTSFOSAFOSAAMe-Et-Σ PFSA Σ PrePFOSRatio ID (A) FOSAA (B)(=A/B) In Lake Sediments (n=10 sampling locations) 24<LOQ<MDL1426110<MDL < LOQ444674153611181.3 25<MDL 652<LOQ<MDL < LOQ6521026.4 26<MDL 541<LOQ<MDL < LOQ541985.5 27<LOQ<MDL1338<LOQ<MDL < LOQ 41013384103.3 28181<MDL1135<LOQ<MDL < LOQ< MDL43213164322.6 29<MDL 1379<LOQ<MDL < LOQ27613792765.0 30<MDL 1070<MDL < LOQ18310701835.9 31<MDL 1886374<MDL < LOQ8971210226021070.9 32<MDL 480<MDL < LOQ4800n.a. 34<LOQ<MDL439<MDL 4390n.a. >LOQ (%)10%0%100%20%0% 20%70% Inland Sediment (Creeks in Industrial Complex, n=10) 2<MDL 742<MDL 1227421226.1 3<MDL 97571056140<MDL10387021797763910813111770.9 4667<MDL8803229<MDL16064110< LOQ580970075311.7 5419<MDL700791195<LOQ22672029322006589271693115506.1 6<MDL 5916279<MDL103952315381214619520792.8 8224<MDL4257439<MDL<LOQ1043992231435492021622.0 10512350102468059372771944331568277832172257875398496.2 11872<MDL36683571<MDL9311047548948333812659076.2 12<MDL 4454<MDL<LOQ<MDL82< LOQ771536445413893.2 1510082702200491266<LOQ 225411451048906825025135151.5 >LOQ (%)60%20%100%80%20%50%90%80% 100% Inland Sediment (Residential Complex, n=4) 17<MDL 880 n.a. 19<MDL 185<MDL < LOQ1131851131.6 20<MDL 1024324<MDL < LOQ1291861408134817220.6 21<MDL 00n.a. >LOQ (%)0% 50%25%0% 25% 75%110.4 Procedural Blanks Sand<MDL n.a. Tube<MDL n.a. LOQ100 150100 150 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 The log-transformed distribution coefficient Kd, was found to be significantly associated with fluorinated carbon number on studied PFCs (0.18 increment per C-F 2 unit addition), but no statistical associations between Kd and salinity were found. Frndlch DataSignif. Cmpdnlog(Kf)r2r2 CountLevel C60.9341.9310.768120.01 C71.0561.8320.2598ns C81.0471.7620.594140.01 C91.5041.9640.523130.01 C101.2922.6180.2848ns Sorption isotherms for PFSAs and PFCAs Freundlich equation: C sed = K f (C w ) n log C sed = nlog C w + log K f Affects of Chain Length and Salinity on Sediment Distribution