Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey

Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey

STOTEN-15762; No of Pages Science of the Total Environment xxx (2014) xxx–xxx Contents lists available at ScienceDirect Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey Nguyen-Hoang Lam a, Chon-Rae Cho b, Jung-Sick Lee a, Ho-Young Soh a, Byoung-Cheun Lee c, Jae-An Lee c, Norihisa Tatarozako d, Kazuaki Sasaki e, Norimitsu Saito e, Katsumi Iwabuchi e, Kurunthachalam Kannan f, Hyeon-Seo Cho a,⁎ a College of Fisheries and Ocean Sciences, Chonnam National University, Yeosu 550-749, Republic of Korea Korea Research Institute of Chemical Technology, Daejeon 305-600, Republic of Korea c National Institute of Environmental Research, Incheon 404-408, Republic of Korea d National Institute for Environmental Studies, Tsukuba, Ibaraki 305-8506, Japan e Research Institute for Environmental Sciences and Public Health of Iwate Prefecture, Iwate 020-0852, Japan f Wadsworth Center, New York State Department of Health, and School of Public Health, State University of New York at Albany, Empire State Plaza, PO Box 509, Albany, NY 12201-0509, USA b H I G H L I G H T S • • • • • PFOS was found at greatest concentrations in water, sediment, plankton and fish High concentrations of long chain PFCAs were found in sediment samples Mean ratios of PFASs concentration in fish blood to liver were mostly N2 PFOS, PFUnA, PFDoA and PFDA accounted for 94–99% of ∑PFASs concentration in fish Only PFOS and PFNA were concentrated in plankton samples a r t i c l e i n f o Article history: Received 30 October 2013 Received in revised form 10 January 2014 Accepted 10 January 2014 Available online xxxx Keywords: Perfluorooctanesulfonate Perfluorinated compounds Korea Freshwater Bioconcentration factor Fish tissues a b s t r a c t Water, sediment, plankton, and blood and liver tissues of crucian carp (Carassius auratus) and mandarin fish (Siniperca scherzeri) were collected from six major rivers and lakes in South Korea (including Namhan River, Bukhan River, Nakdong River, Nam River, Yeongsan River and Sangsa Lake) and analyzed for perfluorinated alkyl substances (PFASs) Perfluorooctane sulfonate (PFOS) was consistently detected at the greatest concentrations in all media surveyed with the maximum concentration in water of 15 ng L−1 and in biota of 234 ng mL−1 (fish blood) A general ascending order of PFAS concentration of water b sediment b plankton b crucian carp tissues b mandarin fish tissues was found Except for the Nakdong River and Yeongsan River, the sum PFAS concentrations in water samples were below 10 ng L−1 The PFOS and perfluorooctanoic acid (PFOA) concentrations in water did not exceed levels for acute and/or chronic effects in aquatic organisms High concentrations of long chain perfluorocarboxylates (LCPFCAs) were found in sediment samples PFOS, perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA) and perfluorodecanoic acid (PFDA) accounted for 94–99% of the total PFASs concentration in fish tissues The mean ratios of PFAS concentration between fish blood and fish liver were above suggesting higher levels in blood than in liver Significant positive correlations (r N 0.80, p b 0.001) were observed between PFOS concentration in blood and liver tissues of both crucian carp and mandarin fish This result suggests that blood can be used for nonlethal monitoring of PFOS in fish Overall, the rank order of mean bioconcentration factors (BCFs) of PFOS in biota was; phytoplankton (196 L/kg) b zooplankton (3233 L/kg) b crucian carp liver (4567 L/kg) b crucian carp blood (11,167 L/kg) b mandarin liver (24,718 L/kg) b mandarin blood (73,612 L/kg) © 2014 Elsevier B.V All rights reserved Introduction The unique properties such as resistance to hydrolysis, photolysis, bio-degradation and thermal stability, in combination with widespread ⁎ Corresponding author Tel.: +82 616597146; fax: +82 61 654 2975 E-mail address: hscho@jnu.ac.kr (H.-S Cho) application of perfluoroalkyl substances (PFASs), made them global pollutants in abiotic and biotic matrices including food stuffs (Picó et al., 2011), human blood (Kannan et al., 2004; Harada et al., 2010), breast milk (Llorca et al., 2010), wildlife such as fish, birds and marine mammals (Giesy and Kannan, 2001), sediment (Nakata et al., 2006), water (Yamashita et al., 2005) and atmosphere (Li et al., 2011) The worldwide distribution of PFASs was reported in urban and remote areas including 0048-9697/$ – see front matter © 2014 Elsevier B.V All rights reserved http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 Please cite this article as: Lam N-H, et al, Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey, Sci Total Environ (2014), http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 N.-H Lam et al / Science of the Total Environment xxx (2014) xxx–xxx deep oceanic water of up to 5000 m (Yamashita et al., 2005) and in polar bears from the Arctic Ocean (Giesy and Kannan, 2001) Due to their persistence and bioaccumulation, some PFASs can elicit harmful effects in terrestrial and aquatic organisms (Lau et al., 2004) Perfluorooctane sulfonate (PFOS) also biomagnifies in wildlife at higher trophic levels in the food chain (Giesy and Kannan, 2001; Kannan et al., 2005) To humans, the major routes of PFAS exposures include diet (Tittlemier et al., 2007; Zhang et al., 2010), drinking water (Takagi et al., 2008; Nolan et al., 2010; Llorca et al., 2012) and indoor dust (Strynar and Lindstrom, 2008; Björklund et al., 2009) Following the discovery of widespread global contamination by PFOS, the M Company, a major producer of this compound, phased out its production in the USA from 2001 (Giesy and Kannan, 2001) Several other countries have put forward some regulations to ban or limit the use of PFASs; for example, in industrial and domestic products in Canada and European Union in 2006 PFOS and, its salts and perfluorooctane sulfonyl fluoride were listed on Annex B of The Stockholm Convention on persistent organic pollutants by the Fourth Conference of Parties in May 2009 (Kannan, 2011) South Korea is a developed and industrialized country PFASs have been used extensively in various industries including electronic and textile industries in South Korea The concentrations of PFASs in surface water from certain industrial areas in South Korea are the highest among several Asian countries as well as globally (Rostkowski et al., 2006; Cho et al., 2010) Previous studies have also reported high accumulation of PFASs in human blood (Kannan et al., 2004; Harada et al., 2010; Ji et al., 2012), birds (Kannan et al., 2002a; Yoo et al., 2008), minke whales and common dolphins (Moon et al., 2010), Asian periwinkles and rockfish (Naile et al., 2010) and coastal and ocean waters from Korea (So et al., 2004; Yamashita et al., 2005; Rostkowski et al., 2006; Naile et al., 2010) Despite this, available studies on PFASs in Korean freshwater ecosystems such as lakes or rivers are limited Here, we carried out a systematic study during 2010 to 2012 to determine the current status and extent of PFAS concentrations in both abiotic and biotic matrices in six major rivers and lakes in Korea Rivers and lakes were surveyed along a spatial gradient representing upstream and downstream locations to identify sources of pollution Accumulation in tissues (blood and liver) of various freshwater aquatic organisms was investigated Materials and methods 2.1 Chemicals and reagents MPFAC-MXA, a mixture of surrogate standards containing 13C4PFOS (sodium perfluoro-1-[1,2,3,4-13C4] octane sulfonate), and 13C4PFOA (Perfluoro-n-[1,2,3,4-13C4]) octanoic acid were purchased with PFAC-MXB, a mixture of 17 native perfluorocarboxylate acids (PFCAs) and perfluoroalkyl sulfonates from Wellington Laboratories (Guelph, ON, Canada) 13C4-PFOS was used as a surrogate for the perfluoroalkyl sulfonates and 13C4-PFOA was used as a surrogate for the PFCAs PFACMXB mixture was used for standard calibration at concentrations ranging from 0.1 to 50 ng/mL High performance liquid chromatography (HPLC) grade reagents including methanol (Kanto Chemical, Tokyo, Japan), water (J.T Baker, USA) and ammonium acetate (Junsei, Japan) were used Milli-Q water was prepared by a Barnstead Nanopure Infinity TM water purification system (Thermo Scientific, USA) 2.2 Sample collection Samples of water, sediment, plankton, and blood and liver tissues of an omnivorous fish species (crucian carp) and a carnivorous fish species (mandarin fish) were collected from 17 sampling sites in six major rivers and lakes in South Korea including Bukhan, Namhan, Nakdong, Nam, Yeongsan Rivers and Sangsa Lake (Fig 1) The Nakdong River, Yeongsan Fig Map showing 17 sampling sites located in six major rivers and lakes from South Korea River and Han River are three of four largest river basins in South Korea and play an important role as a water resource for agriculture, industry, recreational and drinking water for millions of people living in metropolitan cities of Seoul, Daegu, Busan and Gwangju The Bukhan and Namhan Rivers are two major tributaries of the Han River The Nakdong River, and its main tributary, Nam River are located in the southeastern region; the Yeongsan River and Sangsa Lake are located in the southwestern region and the Namhan and Bukhan Rivers are located in the northeastern region of the Korean peninsula The sampling areas were divided generally into groups as highly industrialized areas (Yeongsan River and Nakdong River), moderately industrialized areas (Namhan River and Nam River) and less industrialized areas (Sangsa Lake and Bukhan River) In order to survey the effects of discharge of waste water treatment plant (WWTP) effluents on PFASs concentration in surface water samples, the sampling sites and 13 were from downstream of industrial waste water treatment plants (I-WWTP) in Daegu metropolitan city (treatment capacity of 520,000 ton/day) and in Haman town (treatment capacity of 3400 ton/day), respectively; the sampling sites 16 and 13 were located downstream of domestic waste water treatment plants (D-WWTP) in Gwangju metropolitan city (treatment capacity of 600,000 ton/day) and in Seungju town (capacity of 2500 ton/day), respectively Because the sampling sites were selected to represent Korea, and involved various levels of industrialization, the results of this study represent PFAS concentrations in freshwater ecosystems in Korea One liter clean polypropylene (PP) bottles pre-rinsed with Milli-Q water, methanol and water from a specific sampling site were sunk to collect surface waters Surface layer (1–5 cm) of sediment samples was collected using a clean, methanol rinsed PP spatula and stored in pre-cleaned 50 mL PP tubes Phytoplankton, micro-zooplankton and mesozooplankton samples were collected vertically by using NORPAC® plankton net with mesh sizes of 20, 60, 200 μm, respectively Depending on the depth of water column and topography of fishing sites, fish samples were collected by drift gill net, cast net or fish and hook Fresh blood and liver tissues were obtained from fish Sexes, body weight, body length, hepatosomatic index (HSI) and gonadosomatic index (GSI) of fishes were also determined Water and sediment samples were transported on ice, to the laboratory, and keep at °C until extraction Biota samples were stored in dry ice immediately after collection in the field and kept at −20 °C in the laboratory until extraction Please cite this article as: Lam N-H, et al, Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey, Sci Total Environ (2014), http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 N.-H Lam et al / Science of the Total Environment xxx (2014) xxx–xxx 2.3 Sample extraction and analysis Ten perfluorinated compounds including perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), and perfluorodecane sulfonate (PFDS) were the target analytes in the present study Water samples were not filtered to avoid the loss of some PFASs and potential for contamination of target PFASs from filter papers during the filtration procedure Thus, concentrations reported for water samples represent both dissolved and particulate phase concentrations Sediment samples were air-dried, crushed with pestle and mortar and sieved through a 0.25 mm sieve prior to extraction Water samples were analyzed following the method described by Yamashita et al (2004) Sediment samples were extracted based on the method of Nakata et al (2006) Biota samples were analyzed by ion-pair extraction method described elsewhere (Hansen et al., 2001; Giesy and Kannan, 2001; Hart et al., 2008) Concentrations of PFASs were determined by an Agilent 1100TM HPLC interfaced with Applied Biosystems API 2000TM electrospray ionization tandem mass spectrometer (ESI-MS/ MS) Ten μL aliquot of the extracted sample were injected Flow rate of the mobile phase was 300 μL/min To quantify the target chemicals by MS/MS, a multiple reaction monitoring (MRM) mode was used 2.4 Quality assurance and quality control Procedural blanks were prepared to check for possible contaminations arising from the sample preparation procedure Concentrations of target chemicals were subtracted from concentrations found in blanks, when applicable The regression coefficient (r2) of the calibration curves for all target analytes, prepared at concentrations of 0.1, 0.2, 0.5, 1, 2, 5, 10, 20, and 50 ng/mL was ≥0.99 The detection limits of PFASs in samples ranged from 0.01 to 0.1 ng L−1 for water, 0.01 to 0.02 ng g−1 dry weight (dw) for sediment, and 0.01 to 0.1 ng g−1 wet weight (ww) or ng mL−1for biota The recovery rates (%) of surrogate standards spiked into each sample prior to extraction were in the range of 73.6% to 131% The concentrations of target analytes were not corrected for surrogate recovery rates 2.5 Statistical analysis In this study, the parametric method of regression on order statistics function and the nonparametric method of Kaplan–Meier built in the statistical software of ProUCL 4.1 (U.S Environmental Protection Agency) were utilized to treat the data sets with 0% b % non-detected (NDs) b 80% Alternatively, if the %NDs in a data set exceeded 80% or if the number of distinct observation in a data set was smaller than 5, which is the minimum distinct observation size required to run ProUCL 4.1, all NDs were assigned a value of zero (Singh et al., 2006) Spearman's correlation analysis and Student's t-test were also performed by using SPSS® (IBM, version 21) to investigate correlations and statistical differences between selected data groups Results and discussion The overall observation of all target analytes in various matrices is presented in Table 3.1 PFASs in water Except for the Nakdong River and Yeongsan River, the sum PFAS concentrations in water samples collected in rivers and lakes from Korea were below 10 ng L− (Fig 2) Among PFASs analyzed, PFOA and PFOS were consistently detected at high concentrations in river and lake water samples (Table 2) The mean percentages of PFOA and PFOS concentrations in total PFASs concentration in water were 24% and 37%, respectively The greatest concentrations of PFOA and PFOS were found in the sampling sites and 16, respectively, which are located downstream of industrial and domestic waste water treatment plants (WWTPs) in Daegu and Gwangju metropolitan cities These results suggest that WWTPs are the “point-sources” of aqueous discharges of PFASs into the aquatic environments The ratios of concentration of PFOS to PFOA were in the range of 0.23 to 39 (mean = 4.15), which is comparable to a general concentration ratio of PFOS to PFOA (mean of N4) in water samples from Korean coastal waters (Naile et al., 2010) Apart from the Nam River, where this ratio ranged from 0.23 to 0.30, the PFOS/PFOA concentration ratio in water samples from other freshwater sampling sites was generally greater than This result suggests that except for the Nam River where PFOA was the dominant PFAS, PFOS was dominant in water samples from the other sampling areas Higher concentrations of PFOS and PFOA have been reported in surface waters from some other regions in South Korea and Asia, than those found in the present study In South Korea, the greatest concentrations of PFOS and PFOA were found in water samples collected from the heavily industrialized area of Shihwa Lake High concentrations of PFOS and PFOA in water samples from this “hotspot” were reported by Rostkowski et al (2006) (max PFOS = 651 ng L−1; max PFOA = 61.7 ng L−1; n = 21); Naile et al (2010) (max PFOS = 450 ng L− 1; max PFOA = 68.6 ng L−1; n = 8) and So et al (2004) (mean PFOS = 730 ng L− 1; mean PFOA = 320 ng L− 1; n = 1) Additionally, mean Table Overview of PFASs analysis results Item Water a Sampling site (n) Analyzed sample (n) Detected sample PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFHxS PFOS PFDS Average detected a b c 17 19 n (%) 15 (79) 16 (84) 17 (89) 16 (84) 12 (63) 15 (79) 12 (63) 18 (95) 19 (100) (0) 14 (74) Sediment 17 27 n (%) (22) (11) 24 (89) 24 (89) 24 (89) 23 (85) 27 (100) (33) 27 (100) (0) 17 (62) Plankton b 12 n (%) (0) (0) (0) 10 (83) (8) (50) (58) (0) (50) (0) (25) Carp blood c 69 n (%) (10) (0) 24 (35) 16 (23) 69 (100) 69 (100) 69 (100) 29 (42) 69 (100) (1) 35 (51) Carp liver c 69 n (%) (0) (0) (13) 30 (43) 69 (100) 69 (100) 67 (97) (6) 58 (84) (13) 32 (46) Mandarin blood b 20 n (%) (0) (0) 19 (95) 16 (80) 19 (95) 20 (100) 20 (100) (0) 20 (100) 18 (90) 13 (66) Mandarin liver 2b 20 n (%) (0) (0) (45) (0) (10) 20 (100) 15 (75) (0) 20 (100) (0) (33) Sites and were surveyed in 2010 and others were surveyed in 2012 Collected in sites and Collected in sites 2, 4, 5, 7, 10, 13 and 16 Please cite this article as: Lam N-H, et al, Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey, Sci Total Environ (2014), http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 N.-H Lam et al / Science of the Total Environment xxx (2014) xxx–xxx Concentration (ng/L) 40 30 20 10 Q3 median mean Q1 max Bukhan Namhan Nakdong Nam River name Sangsa Yeongsan Fig Sum PFASs concentrations in water collected from major rivers and lakes in Korea The mean total PFAS concentrations in Bukhan River, Namhan River, Nam River and Sangsa Lake were below 10 ng/L concentrations of PFOS (67.2 ng L−1) and PFOA (32.5 ng L−1) in seawater samples (n = 11) from Korean Western and Southern coast reported by So et al (2004) were higher than those found in freshwater in this study In Japan, mean PFOS concentrations in water samples (n = 14) collected from Tokyo Bay, Osaka Bay and Ariake Bay (Taniyasu et al., 2003) were 1.2–6.7 fold greater than the mean PFOS concentration found in the present investigation Senthilkumar et al (2007) and Lien et al (2008) also reported higher PFOS and PFOA concentrations in river water from Kyoto area and the Yodo River basin in Japan than those found in the present study, but the concentrations were similar to those reported by Sinclair et al (2006) for river and lake waters in New York (USA), So et al (2007) for waters from the Pearl River, Guangzhou and the Yangtze Rivers, Shanghai (China) and Liu et al (2009) for rain and snow from Dailan (China) More detailed comparisons of PFOS and PFOA concentration obtained in water samples from the present study with those reported in previous studies are provided in the Supplementary information PFHxS, PFNA and PFHxA accounted for 12.3%, 6.93% and 6.79% of total PFAS concentrations in water samples, respectively Concentrations of these compounds in water samples in the present study were relatively lower than those reported from the west coast of Korea (Naile et al., 2010) and from Shihwa Lake (Rostkowski et al., 2006) but higher than those reported in water samples from Geonggi Bay (Rostkowski et al., 2006) PFDS was not found in any of water samples, even in downstream sampling sites of domestic and industrial WWTPs in the Nakdong River (no 7), Yeongsan River (no.16), Sangsa Lake (no.17) and Nam River (no.13) This is similar with those described in Naile et al (2010), who reported below method detection limit concentrations for PFDA in the Yeongsan River estuary, the heavily industrialized area of Shihwa Lake and Sinduri Beach The different patterns of concentration of PFASs analyzed in the present study, combined with the comparisons with other previous studies, suggest a site-specific PFAS sources in Korean surface waters Thus, further investigations are needed to identify the sources of PFASs The US EPA's Great Lakes Initiative (GLI, USEPA, 1995) intends to provide both acute and chronic data for the protection of fish, invertebrates, and other aquatic organisms based on the results of toxicity testing with freshwater organisms In this guideline, acute toxicity data from a range of specified taxa was collected to identify a final acute value (FAV) that can protect 95% of test species and the acute criterion or criteria maximum concentration (CMC) was established as equivalent to one-half of the FAV Additionally, within the guideline, the chronic criterion or criteria continuous concentration (CCC) was established to represent a concentration of a chemical such that 95% of the genera tested have greater chronic values Following this guideline, Giesy et al (2010) used data from acceptable tests with freshwater organisms from North America including a variety of genera such as water flea, mussel, spring peeper, planarian, amphipod, rainbow trout, leopard frog, oligochaete, fathead minnow, midge and some sensitive aquatic plants and algae to summarize numerical water quality criteria values for selected PFASs These water quality criteria values were determined as 5.1 μg PFOS/L and 2.9 mg PFOA/L for CCC and 21 μg PFOS/ L and 25 mg PFOA/L for CMC An evaluation of potential ecological risks to aquatic organisms associated with exposure to PFOS and PFOA was employed by comparing the determined concentration of PFOS and PFOA in water samples in the present study with the water quality criteria values for the protection of aquatic organisms reported by Giesy et al (2010) The comparison indicates that PFOS concentrations (up to 15.1 ng L−1) and PFOA concentrations (up to 8.34 ng L−1) found in surface water samples in the present study were 300–300,000 fold less than the reported CMC and CCC values This result suggests that chronic and acute effects on aquatic organisms exposed to PFOS and PFOA in surface waters from the six major rivers and lakes in Korea were not likely Furthermore, the reported water concentration of PFOS that is protective of avian wildlife was also determined to be 47 ng L−1 by Giesy et al (2010) This value was calculated as the geometric mean of three avian wildlife values for herring gull, bald eagle and kingfisher, which were 41 ng PFOS/L, 71 ng PFOS/L and 36 ng PFOS/L, respectively In the present study, the highest concentration of PFOS found in water samples was less than this avian wildlife protection value This result Table Concentration (ng L−1) of PFASs in water showed in min–max (mean) Site (n) PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFHxS PFOS PFDS ∑PFASsa Bukhan (3) 0.11–0.31 (0.18) ND 0.12–0.27 (0.19) ND–0.45 (0.26) 0.71–3.43 (1.85) 0.45–0.91 (0.68) ND–0.18 (0.06) 0.41–0.79 (0.60) ND–3.43 (0.59) 0.56–1.41 (0.94) ND–0.64 (0.20) 3.56–8.34 (6.50) 3.40–4.65 (3.84) 0.29–0.63 (0.43) 2.43–4.66 (3.97) ND–8.34 (2.49) 0.29–0.52 (0.38) ND–0.32 (0.08) 0.83–4.49 (2.32) 0.53–0.69 (0.62) 0.14–0.33 (0.21) 0.54–1.08 (0.85) ND–4.49 (0.71) 0.10–0.21 (0.14) ND–0.11 (0.02) 0.53–4.80 (2.13) 0.19–0.33 (0.26) 0.05–0.07 (0.06) 0.14–1.10 (0.64) ND–4.80 (0.52) 0.19–0.32 (0.24) ND 0.10–0.12 (0.11) ND 0.13–0.33 (0.20) 0.07–0.13 (0.10) 0.06–0.08 (0.06) 0.10–0.31 (0.21) ND–0.33 (0.11) 0.83–1.84 (1.27) 0.67–6.25 (3.30) 6.27–8.46 (7.36) 0.87–1.06 (0.98) 0.25–0.99 (0.59) 1.18–15.07 (11.06) ND–15.07 (3.89) ND 0.28–1.13 (0.59) 0.17–0.21 (0.20) 0.10–0.13 (0.12) 0.13–0.73 (0.41) ND–1.13 (0.25) ND–0.72 (0.39) 0.50–3.97 (2.03) 0.89–1.71 (0.21) 0.23–0.37 (0.32) 0.03–0.11 (0.07) 0.42–1.63 (1.03) ND–3.97 (0.90) Namhan (4) Nakdong (3) 0.51–7.94 (3.82) Nam (3) 0.86–1.31 (1.03) Sangsa (3) 0.02–0.18 (0.10) Yeongsan (3) 0.93–1.33 (1.11) All sampling sites ND–7.94 (19) (0.98) ND ND ND ND ND ND 2.31–5.71 (3.85) 1.17–10.86 (5.90) 14.71–40.63 (26.00) 7.09–9.61 (8.01) 1.51–1.83 (1.70) 8.47–25.19 (18.68) 1.17–40.63 (10.44) n: number of analyzed sample; ND: below the method detection limit a ∑PFASs refer to sum of ten detectable PFAS in each sampling site Please cite this article as: Lam N-H, et al, Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey, Sci Total Environ (2014), http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 ND ND ND ND ND ND ND 0.01–0.07 (0.04) 0.02–0.048 (0.18) 0.04–0.27 (0.16) 0.02–0.12 (0.05) 0.04–0.04 (0.04) 0.05–0.11 (0.07) 0.01–0.48 (0.12) ND–0.01 (0.01) ND ND–0.01 (0.00) ND–0.01 (0.00) 0.01–0.01 (0.01) ND–0.01 (0.00) ND–0.01 (0.00) 0.02–0.11 (0.07) 0.01–0.04 (0.03) 0.07–0.08 (0.08) 0.06–0.13 (0.09) 0.06–0.09 (0.07) 0.06–0.08 (0.07) 0.01–0.13 (0.05) ND–0.08 (0.04) ND–0.08 (0.04) 0.03–0.08 (0.06) 0.04–0.09 (0.06) 0.02–0.03 (0.03) 0.02–0.04 (0.03) ND–0.09 (0.04) ND–0.03 (0.01) 0.01–0.08 (0.03) 0.02–0.07 (0.05) ND–0.04 (0.02) ND–0.04 (0.02) 0.03–0.04 (0.03) ND–0.08 (0.03) ND–0.03 (0.02) ND–0.05 (0.01) ND–0.01 (0.01) ND ND ND ND–0.05 (0.01) Bukhan (3) Namhan (12) Nakdong (3) Nam (3) Sangsa (3) Yeongsan (3) All sampling sites (27) n: number of analyzed sample; ND: below the method detection limit a ∑PFASs refer to sum of ten detectable PFAS in each sampling site ND–0.05 (0.02) ND–0.12 (0.02) ND–0.03 (0.01) ND–0.10 (0.06) ND–0.09 (0.04) 0.09–0.15 (0.12) ND–0.15 (0.04) ND–0.09 (0.04) 0.03–0.28 (0.07) 0.04–0.08 (0.06) 0.03–0.09 (0.05) 0.02–0.03 (0.03) ND–0.05 (0.02) ND–0.28 (0.05) PFOS PFHxS PFDoA PFUnA PFDA PFNA PFOA PFHpA PFHxA Site (n) Table Concentration (ng g−1dw) of PFASs in sediment showed in min–max (mean) The distribution of PFASs concentration in sediment samples is summarized in Table Approximately 2/3 of the sediment samples analyzed in this study contained PFASs above the detection limits Similar to that in water samples, PFDS was not detected in any of sediment samples (Table 1) PFOS and PFDoA were found in all analyzed sediment samples Mean PFOS concentration in sediments was 0.12 ng g−1 dw, which accounted for 32% of the total PFAS concentrations in sediments The measured PFOS concentrations from sediments in the present study were lower than those reported previously from Korean western coasts (Naile et al., 2010; = ng g−1 dw), Roter Main River in Germany (Becker et al., 2008; mean = 0.21 ng g−1 dw), Dailao River system in China (Bao et al., 2009; mean = 0.21 ng g−1 dw), Yangtze River estuary in China (Pan and You, 2010; mean = 536 ng g−1 dw), Tokyo Bay in Japan (Sakurai et al., 2010; mean = 0.54 ng g−1 dw) and San Francisco Bay in the USA (Higgins et al., 2005; mean = 0.85 ng g− dw), but were comparable with those described from Liao River in China (Yang et al., 2011; mean = 0.15 ng g − dw), Taihu Lake in China (Yang et al., 2011; mean = 0.15 ng g− dw) and Southern Rivers of Japan (Nakata et al., 2006; range: 0.09–0.14 ng g − dw) PFDoA (mean = 0.05 ng g− dw) was the next predominant PFAS found in the sediments PFDoA levels in sediments were 13 to 48 fold lower than those from Uji River (mean = 0.75 ng g− dw), Tenjin River (mean = 2.4 ng g− dw), or in Kamo River (0.94 ng g− dw), and Katsura River (1.7 ng g− dw) in Japan (Senthilkumar et al., 2007), but were higher than those from Liao River (mean = 0.01 ng g−1 dw) and Taihu Lake (mean = 0.03 ng g−1 dw) in China (Yang et al., 2011) Following PFDoA, PFOA was found as the next dominant PFAS in the sediments Detailed comparisons of PFOS and PFOA concentration found in the present study with those reported in previous studies are provided in the Supplementary information Similar to PFDoA and PFOA, other long-chain perfluorocarboxylates (LCPFCAs) including PFNA, PFDA and PFUnA were detected in sediments with high detection frequency (Table 1) This result is comparable with that in sediment samples from the Liao River and Taihu River, China (Yang et al., 2011) High percentages of mean concentrations of these LCPFCAs to total PFASs concentration in sediment samples were found consistently in all studied rivers and lakes at 71.8%, 50.6%, 63.3%, 85.2%, 79.1% and 79.8% in Bukhan River, Namhan River, Nakdong River, Nam River, Sangsa Lake and Yeongsan River, respectively This result suggests that these LCPFCAs are dominant chemicals for sorption process on freshwater sediment samples in the present study Partition coefficients of PFASs between sediment and surface water (Kd), which is estimated by the ratio of the concentration of PFASs in the sediment (ng g−1dw) to the concentration of PFASs in the overlying water (ng/L) at the same sampling sites, were used to evaluate PFASs distribution patterns in the sediment samples The mean Kd values are summarized in Table An ascending order of mean Kd for LCPFCAs of PFOA (0.04) b PFNA (0.10) b PFDA (0.13) b PFUnA (0.21) b PFDoA (0.72) was found The positive association between Kd value with the number of perfluorocarbon chain length obtained in the present study is consistent with that described by Higgins and Luthy (2006) It is worth noting that Higgins and Luthy (2006) reported that perfluorocarbon chain length was the dominant structural feature influencing sorption, with each CF2 moiety contributing 0.50–0.60 log units to the measured freshwater–sediment distribution coefficients of perfluorinated surfactants However, PFOS and PFOA had different Kd values Mean Kd value for PFOS was higher than that for PFOA in most sampling sites This difference may be caused by the effect of the sulfonate moiety, which contributed an additional 0.23 log units to the measured distribution coefficient, when compared to carboxylate analogs (Higgins and Luthy, 2006) PFDS 3.2 PFASs in sediment ND ND–0.06 (0.01) ND ND ND ND ND–0.06 (0.00) ∑PFASsa indicates that the concentrations of PFOS in water samples from all sampling sites in the present study are unlikely to cause potential harmful effects to avian wildlife 0.03–0.40 (0.25) 0.12–1.09 (0.39) 0.21–0.55 (0.43) 0.17–0.57 (0.35) 0.20–0.25 (0.23) 0.33–0.36 (0.35) 0.03–1.09 (0.35) N.-H Lam et al / Science of the Total Environment xxx (2014) xxx–xxx Please cite this article as: Lam N-H, et al, Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey, Sci Total Environ (2014), http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 N.-H Lam et al / Science of the Total Environment xxx (2014) xxx–xxx Table Mean partition coefficients (Kd) of PFASs between sediment and surface water Site (n) PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFHxS PFOS PFDS Bukhan (3) Namhan (2) Nakdong (3) Nam (3) Sangsa (3) Yeongsan (3) All sampling sites (17) 0.09 – – – – – – – 0.06 0.12 0.01 0.01 0.07 0.01 0.04 0.03 – 0.01 0.10 0.26 0.16 0.10 0.10 0.15 0.05 0.09 0.29 0.09 0.13 0.18 – 0.17 0.31 0.24 0.14 0.21 0.63 – 0.46 0.98 1.11 0.44 0.72 0.01 0.00 – 0.01 0.13 – 0.03 0.04 0.16 0.02 0.06 0.09 0.02 0.07 – – – – – – – – – – – 0.02 n: number of sampling site 3.3 PFASs in biota The concentration profiles of PFASs in plankton samples are shown in Table PFHxA, PFHpA, PFOA, PFHxS, and PFDS were not detected in any plankton samples Despite the highest detection frequency of PFNA (83%), the greatest mean PFASs concentration was observed for PFOS (2.08 ng PFOS/g ww) in plankton samples It is worth to note that the next greatest mean PFAS concentration was for PFDoA at 0.36 ng g−1ww, which was approximately 6-fold less than the mean concentration of PFOS The mean concentrations of remaining PFASs were in the order of PFNA N PFUnA N PFDA N PFDoA Very few studies have measured PFASs in plankton The mean concentration of PFOS in zooplankton samples analyzed in this study was relatively less than that reported from China (Li et al., 2008; 4.18 ng g−1ww), or from the Barents Sea (Haukås et al., 2007; mean = 3.85 ng g−1ww) but was higher than that reported from Western Arctic (Powley et al., 2008; max = 0.2 ng g−1ww) and Eastern Arctic (Tomy et al., 2004; mean = 1.8 ng g−1ww) PFNA was not detected in zooplankton samples from the Barents Sea (Haukås et al., 2007) but was found in a sample from Beijing, China (Li et al., 2008; 0.15 ng g− 1ww) Although PFOA was not detected in any plankton samples in the present study and in zooplankton samples from Bank Island, Western Arctic (Powley et al., 2008), this chemical was found at relatively high concentration in zooplankton collected from Frobisher Bay (Tomy et al., 2004; mean = 2.6 ng g− 1ww), Barents Sea (Haukås et al., 2007; mean = 3.15 ng g− ww) and Gaobeidian Lake (Li et al., 2008; mean = 0.05 ng g− 1ww) Concentrations of PFASs in blood and liver of crucian carp and mandarin fish are summarized in Table PFHpA was not detected in all investigated fish tissues PFOS was consistently found at the highest concentration and accounted for 37%, 57%, 49% and 52% of the total PFASs concentration in crucian carp blood, crucian carp liver, mandarin fish blood and mandarin fish liver, respectively Following PFOS, PFUnA was the next predominant PFAS in fish tissues PFOS and PFUnA were also reported as the predominant PFASs found in both liver samples from marine mammals from Korean coastal waters (Moon et al., 2010) and skipjack tuna collected from offshore waters and some open ocean sites in the Sea of Japan, the East China Sea, the Indian Ocean, and the Western North Pacific Ocean (Hart et al., 2008) In the present study, PFUnA was found in all fish tissues samples The detecting frequency of PFOS and PFDoA was 100% in crucian carp and mandarin fish blood samples and the detecting frequency of PFDA was 100% in crucian carp blood and liver samples The sum concentrations of these Table Concentration of PFASs in plankton samples (ng g−1ww) showed in min–max (mean) Sampling media (n) PFNA PFDA PFUnA PFDoA PFOS ∑PFASsa Phytoplankton (4) Micro-zooplankton (4) Meso-zooplankton (4) 0.30–0.50 (0.43) ND–0.40 (0.20) ND–0.50 (0.25) ND–0.39 (0.10) ND ND ND–0.27 (0.13) ND–0.44 (0.17) ND–0.27 (0.10) ND–0.71 (0.26) ND–0.96 (0.43) ND–1.08 (0.39) ND–0.70 (0.21) ND–11.07 (2.82) ND–12.67 (3.21) 0.30–2.15 (1.12) 0.10–12.47 (3.61) 0.20–12.98 (3.94) n: number of analyzed sample; ND: below the method detection limit a ∑PFASs refer to sum of ten detectable PFAS in each sampling site Table Range and mean concentration (ng g−1ww or ng mL−1) of PFASs in fish tissues Crucian carp (n = 69) Mandarin fish (n = 20) f/m (n.d.)* BW (g) BL (cm) HSI GSI 50/18 (1) 76.40 ∼ 973.19 (237.74) 12.50 ∼ 32.00 (19.40) 0.45 ∼ 7.71 (2.93) 0.29 ∼ 16.23 (5.05) 12/7 (1) 52.58 ∼ 424.60 (134.85) 15.20 ∼ 29.40 (19.27) 0.79 ∼ 3.01 (1.67) 0.09 ∼ 2.77 (0.63) Concentration Blood Liver Blood Liver PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFHxS PFOS PFDS ∑PFASs** ND ∼ 0.36 (0.02) ND ND ∼ 0.89 (0.09) ND ∼ 13.22 (1.46) 0.44 ∼ 20.58 (5.15) 0.88 ∼ 45.16 (7.11) 0.11 ∼ 19.18 (3.20) ND ∼ 4.96 (0.17) 0.18 ∼ 145.23 (13.93) ND ∼ 0.60 (0.04) 1.72 ∼ 236.29 (31.18) ND ND ND ∼ 0.33 (0.03) ND ∼ 0.86 (0.07) 0.06 ∼ 3.48 (0.75) 0.04 ∼ 5.01 (0.80) ND ∼ 2.08 (0.43) ND ∼ 0.30 (0.01) ND ∼ 43.76 (6.15) ND ∼ 0.58 (0.05) 0.15 ∼ 54.64 (8.29) ND ND 0.06 ∼ 0.34 (0.19) 0.03 ∼ 1.00 (0.21) ND ∼ 28.33 (12.20) 9.98 ∼ 52.39 (20.32) 3.10 ∼ 13.94 (6.74) ND 3.68 ∼ 233.68 (60.62) 0.08 ∼ 1.27 (0.44) 31.08 ∼ 296.72 (100.72) ND ND 0.09 ∼ 0.33 (0.13) ND 0.38 ∼ 5.78 (1.68) 1.93 ∼ 8.04 (4.53) 0.92 ∼ 3.17 (1.76) ND 1.61 ∼ 114.99 (19.38) ND ∼ 0.23 (0.01) 6.13 ∼ 131.58 (6.13) BW: body weight; BL: body length; ND: below the method detection limit; n: number of analyzed sample a f/m (n.d.): female/male (not determined) b ∑PFASs refer to sum of ten detectable PFAS in each individual fish Please cite this article as: Lam N-H, et al, Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey, Sci Total Environ (2014), http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 PFOS PFHxA PFDA PFHpA PFUnA PFOA PFDoA PFHxS PFNA PFDS Mandarin liver Mandarin blood Carp liver 60 PFDA PFOS 40 20 0 100 0% 40% 60% 80% 100% Fig Patterns showing relative concentrations of individual PFASs (mean-%-composition) in the surveyed fish tissues PFOS, PFUnA, PFDA and PFDoA were predominant PFASs in the fish tissues and accounted averagely for 97.47% of total PFASs concentration 40 (Taniyasu et al., 2003) Furthermore, physiological conditions (e.g., reproductive stages) may play a role in the alteration of blood to liver ratios in concentrations of PFASs (Kannan, 2011) A significant negative correlation was observed between HSI and blood to liver ratio of PFOS and PFNA (p b 0.05) in crucian carp The blood to liver concentration ratio of PFOS and PFNA, thus, decreased with increasing HSI in crucian carp A significant positive correlation was found between GSI and blood to liver ratio of PFOS (p b 0.05) in mandarin fish The blood to liver ratio of PFOS, therefore, increased with increasing sexual maturity of mandarin fish, which is represented by GSI Some previous studies have reported gender-specific differences in the PFAS concentrations in aquatic animals (Keller et al., 2005; Kannan et al., 2002b) In the present study, there was no significant difference (p N 0.05) in all PFAS concentrations between sexes of fish tissues except for PFNA in mandarin fish blood The PFNA concentration in female mandarin fishes was significantly greater than that in males (p b 0.05) PFNA was also the only PFAS that has the significant positive correlation with crucian carp body weight and body length (p b 0.05) These results suggest different PFAS composition profiles in the surveyed fish and chemical compound-specific, fish species-specific and tissue-specific bioaccumulation of PFASs 3.4 Bioconcentration factor (BCF) Mean BCFs of PFASs in biota are shown in Table An increasing level of mean concentrations of PFOS was found in biota with the increase in PFOS 100 PFDA 75 50 25 0 20% 20 Fig Relationship between PFOS, PFDA concentrations in blood and those in liver in crucian carp (Spearman's correlation, n = 69, rPFOS = 0.953, pPFOS b 0.001; rPFDA = 0.494, pPFDA b 0.001) Carp blood 200 Blood concentration (ng/ml) Liver concentration (ng/g ww) dominant PFASs including PFOS, PFUnA, PFDoA and PFDA accounted for 94–99% of the total PFASs concentration in fish (Fig 3) The concentrations of PFOS in fish blood ranged from 0.18 to 145 ng mL−1 (mean = 13.9 ng mL−1) in crucian carp and from 3.68 to 234 ng mL−1 (mean = 60.6 ng mL−1) in mandarin fish The next abundant PFASs were in the order of, PFUnA (mean = 7.11 ng mL−1) N PFDA (mean = 5.13 ng mL− 1) N PFDoA (mean = 3.2 ng mL− 1) in crucian carp blood and at mean concentration of 20.3 ng mL− N 12.2 ng mL−1 N 6.74 ng mL−1 in mandarin fish blood Mean PFOS concentrations in fish blood analyzed in this study were relatively lower than those reported for blood of mullet from Shihwa Lake, Korea (Yoo et al., 2009); crucian carp and common carp from Gaobeidian Lake, China (Li et al., 2008); a variety of fish collected from Tokyo Bay, Osaka Bay, Biwa Lake in Japan (Taniyasu et al., 2003); dolphin and bluefin tuna from Italian coast (Kannan et al., 2002b) but higher than those in the blood of shad from Shihwa Lake, Korea (Yoo et al., 2009); and white semiknife carp, tilapia and leather catfish in China (Li et al., 2008) The profiles of PFOS concentration in fish liver varied widely The maximum concentration of PFOS in fish liver was 115 ng g−1ww in a mandarin fish liver sample The mean concentration of PFOS in fish liver samples and other aquatic animals collected from Korea (Moon et al., 2010), Japan (Taniyasu et al., 2003) or the USA (Sinclair et al., 2006) was relatively higher than that found in the present study PFOS concentrations from skipjack tuna in the oceans (Hart et al., 2008) and PFDA, PFUnA and PFDoA concentrations in fish liver from Korea (Yoo et al., 2009) were higher than those reported for crucian carp but lower than those reported for mandarin fish in the present study PFNA concentration found in fish liver tissues in the present study was lower than that reported for rockfish, shad and mullet from Korea (Yoo et al., 2009) More detail comparisons of PFOS and PFOA concentrations obtained in biota sample from the present study with those reported in previous studies are provided in the Supplementary information Significant positive correlations (p b 0.001) between PFAS concentrations in blood and corresponding concentrations in liver were found for PFOS and PFDA in both crucian carp and mandarin fish (Figs and 5) Additionally, Spearman's correlation analysis showed the significant positive correlation between concentrations among PFOA, PFNA, PFDA, PFUnA, PFDoA, PFDS (p b 0.01) and PFHxS (p b 0.05) in crucian carp blood and liver However, strong significant correlations (p b 0.01 and r N 0.8) between PFASs concentration in fish blood and liver were only observed for PFOS, PFUnA, PFDoA in crucian carp and PFOS in mandarin fish These results suggest that blood can be used for nonlethal monitoring of PFASs in fishes The ratio of PFAS concentrations in fish blood to corresponding concentrations in fish liver varied widely The ratio of PFOS concentration in blood to liver varied from 0.71 to 5.17 (mean = 2.31) in crucian carp and from 0.75 to 12.5 (mean = 4.81) in mandarin fish These observations suggest a non-equilibrium in PFAS concentrations between liver and blood of fish, and indicate an ongoing exposure of fish to PFASs Liver concentration (ng/g ww) N.-H Lam et al / Science of the Total Environment xxx (2014) xxx–xxx 100 200 300 20 40 Blood concentration (ng/ml) Fig Relationship between PFOS, PFDA concentrations in blood and those in liver in mandarin fish (Spearman's correlation, n = 20, rPFOS = 0.880, pPFOS b 0.001; rPFDA = 0.675, pPFDA = 0.001) Please cite this article as: Lam N-H, et al, Perfluorinated alkyl substances in water, sediment, plankton and fish from Korean rivers and lakes: A nationwide survey, Sci Total Environ (2014), http://dx.doi.org/10.1016/j.scitotenv.2014.01.045 N.-H Lam et al / Science of the Total Environment xxx (2014) xxx–xxx Table Mean bioconcentration factor of PFASs (L/kg) in biota PFASs Phyto-plankton Microzoo-plankton Mesozoo-plankton Carp liver Carp blood Mandarin liver Mandarin blood PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFHxS PFOS PFDS – – – 1449 – – – – 196 – – – – – – – – – 3017 – – – – 1562 – – – – 3450 – – – 134 150 5957 1877 1945 4572 – 125 – 611 4686 34,896 17,328 11,988 342 11,167 – – – 601 – 7238 – – – 24,718 – – – 739 855 89,216 – – – 73,612 – trophic level in the food chain The BCF of PFOS (concentration in biota/ concentration in water) was as follows: phytoplankton (196 L/kg) b zooplankton (3233 L/kg) b crucian carp liver (4567 L/kg) b crucian carp blood (11,167 L/kg) b mandarin liver (24,718 L/kg) b mandarin blood (73,612 L/kg) This result was consistent with that reported in earlier studies which reported the positive correlations of PFOS concentrations in biota with the increase in trophic level in the food chain (Giesy and Kannan, 2001; Martin et al., 2004; Tomy et al., 2004; Li et al., 2008) Mean BCFs of all investigated PFASs in fish blood were higher than those in fish liver The average BCF of PFOS in fish tissues in this study was relatively higher than those reported in a variety of fishes and some other aquatic animals in both field and laboratory studies (3M, 2003; Moody et al., 2002; Morikawa et al., 2006) Although PFOS concentrations in water samples were comparable with PFOA concentrations, the BCFs of PFOA in biota were 18–100 fold less than those of PFOS Apart from PFOS, only PFNA was concentrated in plankton samples The BCFs of PFNA in phytoplankton and zooplankton were 1449 (L/kg) and 1312 (L/kg), respectively Conclusions The results of this study indicate a general ascending order of PFAS concentration in freshwater aquatic ecosystem comprising water, sediment, plankton, crucian carp tissues, and mandarin fish tissues PFOS was consistently detected at the greatest concentrations throughout the investigated media No potential chronic and/or acute effects on aquatic organisms due to PFOS and PFOA levels measured in surface waters from the six major rivers and lakes were expected The rank order of mean BCF of PFOS in biota was; phytoplankton b zooplankton b crucian carp liver b crucian carp blood b mandarin fish liver b mandarin fish blood The data from the present study also demonstrate that PFOS and LCPFCAs have high BCFs in crucian carp tissues; only PFOS and PFNA were concentrated in plankton samples Different PFAS composition patterns in fish tissues suggest species-specific and tissue-specific bioaccumulation The profiles of occurrence and spatial distribution of PFASs in various environmental media suggest the existence of several sources of PFASs and the continuing input PFASs in Korean rivers and lakes WWTP discharges are a source of PFASs in freshwater ecosystems in South Korea Further study should focus on identifying the existence and status of PFASs sources in South Korean freshwater ecosystems Conflict of interest The authors declare no conflict of interest 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