In-situ partitioning behavior of perfluorinated compounds along a salinity gradient from estuarine and coastal areas of Korea Jong Seong Khim1,#,*, Seongjin Hong1,#, Jinsoon Park1,#, Jonathan E. Naile2, Garry Codling2, John P. Giesy2 1 Division of Environmental Science and Ecological Engineering, Korea University, Seoul, South Korea 2 Department of Veterinary Biomedical Sciences and Toxicology Centre, University of Saskatchewan, Saskatoon, SK, Canada # Present Address: School of Earth and Environmental Sciences, College of Natural Sciences, Seoul National University, Seoul, South Korea *Corresponding author. E-mail: jskocean@snu.ac.kr (J.S. Khim), Presenter. E-mail: hongseongjin@gmail.com (S. Hong) Study area Distribution and concentration of PFASs Figure 1 Sampling sites of the (a) Youngsan and (b) Nakdong River Estuaries, South Korea. • Concentration, distribution, fate, and partitioning of perfluoroalkyl substances (PFASs) were investigated. • Surface water were collected in artificial lakes (n = 5), inland creeks (n = 14), and estuarine areas (n = 14). • Thirteen individual PFASs in water and suspended solids were quantified by use of HPLC-MS/MS. • • • • PFASs widely distributed in waters of estuarine and coastal areas of Youngsan and Nakdong watershed. Concentrations of PFASs were greater at inland sites and artificial lakes than in the estuarine areas. Some inland sites seemed to be affected by industrial activities and wastewater treatment plant outfall. It is indicated that PFASs are mainly transported to estuarine area via the inland waterways (creeks). Fate of PFASs: Youngsan & Nakdong Estuaries Figure 2 Concentration and distribution of (a) dissolved and (b) particulate PFASs. Partitioning behavior of PFASs with salinity Figure 4 Relationships between salinity and partitioning coefficients (Kd) of selected PFASs. Figure 3 Water quality parameters and concentrations of PFASs from (a) Youngsan and (b) Nakdong River Estuaries. Comparison to other toxic chemicals • PFASs were transported to outer region primarily by water discharged during rainy season. • Field-based partition coefficients (Kd) for long-chain PFASs were significantly correlated with salinity; Kd values increased exponentially as a function of salinity. • Due to the “salting-out” effect, PFASs were largely scavenged by adsorption onto suspended solids and/or sediments in estuarine environments. Relationship between Kd and C number Table 1 Estimates of freshwater partitioning (Kd0) and adsorption salting constants (δ) for water-particle partition data reported in the previous study (updated from Tuner and Rawling, 2001). Field /Lab Salinity SS (mg L-1) Kd0 (L kg-1) δ (L mol-1) r2 References PFOA Field 0.12 – 29 8.1 – 130 2.43 1.34 0.48 This study PFNA Field 5.47 1.83 0.66 PFDA Field 11.3 1.85 0.73 PFUnA Field 12.2 1.53 0.65 PFDoA Field 8.62 1.63 0.50 PFOS Field 7.10 2.57 0.72 PFDS Field 13.6 1.53 0.54 PFOA Lab. 751 0.86 0.93 PFDA Lab. 1006 0.94 0.99 PFUnA Lab. 1640 1.11 0.99 PFOS Lab. 1430 0.93 0.94 60.2 0.480 0.52 243 0.366 0.60 0.860 0.341 0.94 0.790 0.091 0.98 241 0.333 - 1.8 0.275 - Compounds PFASs 10 – 34 500 [1] Organochlorines 2,2’,5,5’-Tetrachloro biphenyl Field 2,3,7,8-tetrachlorodibenzodioxin Field Endrin Lab. Heptachlor epoxide Lab. 0.3 – 23.8 5 – 36 ~200 1000 [2] [3] Figure 5 Relationships between log Kd and number of carbon chains for (a) PFCAs and (b) PFSAs. [4] • Values for Kd of PFASs were directly proportional to the number of carbon atoms. • Salting constants of selected PFASs were notably greater than those of other toxic substances. • Overall, the results of the present study provided better understanding of the fate and transport of PFASs in the zone of salinity boundary that can be used in developing fate models of PFASs in the coastal marine environment. Polycyclic aromatic hydrocarbons Benzo(a)pyrene Field 0 – 35 10800 Phenanthrene Field Pyrene Field ~0 – 32 ~100000 2.09 – 3.14 0.552 >0.88 [5] Field 0.4 – 23.8 ~250 – 300 49.9 1.08 0.75 [6] Phthalate Di(2-ethylhexyl)phthalate