Survey of perfluoroalkyl substances concentration and their bioaccumulation in fish from two urban lakes, Ha Noi, Vietnam

Abstract. Twelve perfluoroalkyl substances (PFASs) were investigated in fish samples collected in West Lake and Yen So Lake. Six PFASs including five perfluoroalkylcarboxylic acids (PFCAs) and only one perfluoroalkyl sulfonates acids (PFSAs) compounds were found in fish samples in both lakes. The concentration of long-chain carbon compounds such as PFNA, PFDA, PFUdA and PFDoA were predominant in the entire both lakes. The highest PFASs concentration was found in catfish (1.98 ng.g-1 w.w). The bioconcentration factor (BCF) of PFDoA were the highest in both lakes (854.48 - 3742.68), whereas PFOA‟s BFC values were the lowest in both lakes (2.19 - 27.48). In PFCAs group, BFC values increased with the carbon chain length but with the same carbon chain length PFOS‟s BCF value were higher than PFOA„s.

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36 HNUE JOURNAL OF SCIENCE DOI: 10.18173/2354-1059.2017-0052 Chemical and Biological Science 2017, Vol. 62, Issue 10, pp. 36-43 This paper is available online at SURVEY OF PERFLUOROALKYL SUBSTANCES CONCENTRATION AND THEIR BIOACCUMULATION IN FISH FROM TWO URBAN LAKES, HA NOI, VIETNAM Nguyen Thuy Ngoc, Phan Thi Lan Anh, Phan Dinh Quang, Truong Thi Kim, Tran Thi Mai, Duong Hong Anh and Pham Hung Viet VNU Key Laboratory of Analytical Technology for Environmental Quality and Food Safety Control (KLATEFOS), University of Science, Vietnam National University, Hanoi Abstract. Twelve perfluoroalkyl substances (PFASs) were investigated in fish samples collected in West Lake and Yen So Lake. Six PFASs including five perfluoroalkylcarboxylic acids (PFCAs) and only one perfluoroalkyl sulfonates acids (PFSAs) compounds were found in fish samples in both lakes. The concentration of long-chain carbon compounds such as PFNA, PFDA, PFUdA and PFDoA were predominant in the entire both lakes. The highest PFASs concentration was found in catfish (1.98 ng.g -1 w.w). The bioconcentration factor (BCF) of PFDoA were the highest in both lakes (854.48 - 3742.68), whereas PFOA‟s BFC values were the lowest in both lakes (2.19 - 27.48). In PFCAs group, BFC values increased with the carbon chain length but with the same carbon chain length PFOS‟s BCF value were higher than PFOA„s. Keywords: PFASs, LC-MS/MS, fish, urban lake, West Lake, Yen So, Hanoi. 1. Introduction PFASs are a group of anthropogenic compounds that are known as new persistent organic pollutants (POPs) with special surface-active properties [1]. Their molecular contains two both lipophilic and hydrophilic groups at both sides. PFASs have been manufactured since the late 1940s [1, 2]. Then they have been widely applied in industrial and commercial products such as refrigerants, surfactants, and polymers and as components of pharmaceuticals, fire retardants, lubricants, adhesives, cosmetics, paper coatings, and insecticides because of their extremely strong carbon – fluorine bonds [3]. These compounds are now common contaminants in wastewater because of their widespread occurrence in the environment and their ability to bioaccumulation [4]. They are toxic and carcinogenic to animals such as rats, fishes, monkeys, and even humans [4-7]. Received November 17, 2017. Revised December 7, 2017. Accepted December 14, 2017. Contact Pham Hung Viet, e-mail address: phamhungviet@hus.edu.vn Survey of perfluoroalkyl substances concentration and their bioaccumulation in fish 37 The concern about their presence in the environmental and potential human exposure is rising all over the world. A great number of studies have been available on the contaminations of PFASs in rivers, lakes, and ocean waters and even in air [8, 9], dust[10]. PFASs have been investigated widely in fish of Europe and Asia, such as: Spain [11] Norway [12], Greece [13], Italy[14], Korea [15], and China[16]. However, there is a lack of data of these chemical in fish and the potential exposure to humans in Vietnam. The widespread distribution of PFASs in other environment samples in Hanoi, Vietnam that is still limited investigation. This research investigates the occurrence of 12 PFASs in freshwater cultured fish from two large lakes in Hanoi, Vietnam. The fish samples had been sampling in the interval time of two seasons in the Northern of Vietnam. For fish sampling, the three to four special fresh water species was collected which have been cultivating in these lakes. The PFASs in pretreated samples were analyzed using high performance liquid chromatography-tandem mass spectrometry (LC/MS-MS). The obtained results showed a sufficient picture of the distribution and accumulation of PFASs in fish, the bioaccumulation of PFASs from water to fish and presented the initial health risk assessment for inhabitants using these fishes for meal, correspondingly. 2. Content 2.1. Materials and methods 2.1.1. Chemicals Table 1. List of target PFAS compounds PFACMXB0614 MPFACMXA0714 Compound Abbreviation Compound Abbreviation Perfluorohexansunfonate - 13 C, 18 O MPFHxS Perfluorobutanoic acid PFBA Perfluorooctansunfonate - 13 C, 18 O MPFOS Perfluoropentanoic acid PFPeA Perfluorobutanoic acid - 13 C MPFBA Perfluorohexanoic acid PFHxA Perfluorohexanoic acid - 13 C MPFHxA Perfluoroheptanoic acid PFHpA Perfluorooctanoic acid - 13 C MPFOA Perfluorooctanoic acid PFOA Perfluorononanoic acid - 13 C MPFNA Perfluorononanoic acid PFNA Perfluorodecanoic acid - 13 C MPFDA Perfluorodecanoic acid PFDA Perfluoroundecanoic acid - 13 C MPFUdA Perfluoroundecanoic acid PFUdA Perfluorododecanoic acid - 13 C MPFDoA Perfluorododecanoic acid PFDoA Perfluorobutansunfonate L-PFBS Perfluorohexansunfonate L-PFHxS Perfluorooctansunfonate L-PFOS N. T. Ngoc, P. T. L. Anh, P. D. Quang, T. T. Kim, T. T. Mai, D. H. Anh and P. H. Viet 38 The mixture of PFCAs and PFSAs (PFACMXB0614) and the mixture of Mass- Labeled PFCAs and PFSAs (MPFACMXA0714) were obtained from Wellington Laboratories, Canada. All analyzed PFASs compounds and their abbreviations are showed in table 1. All solvents used in this study were of LC-MS grade. Ammonium acetate was obtained from Wako Chemicals, Japan. Ultrapure water was delivered by a Direct-Q water purification system (Millipore, Japan). HPLC-grade methanol was purchased from Merck, Germany and other chemicals were of analytical reagent grade. 2.1.2. Sampling site Figure 1 shows the location of sampling sites. Two biggest reservoirs, West Lake and Yen So lake, are representative of other freshwater reservoirs in Hanoi. West lake is the largest freshwater lake in the Northeastern of Hanoi city with a shore length of 17km and an area of 530 hectares. This lake is a famous place for recreation with many surrounding gardens, pagodas, hotels, villas and other entertainment places. Yen So lake is a complex of small and big reservoirs that is lying in the Southern of Hanoi with a water area of 70 hectares. This lake is the largest reservoir collecting all municipal wastewater of Hanoi city. Figure 1. Sampling site in Hanoi 2.1.3. Sample collection and preparation The targeted fish species in lakes are carp, mud carp, catfish and hypophtalmichthys that are popular freshwater fishes in Northern of Vietnam. In West Lake, three fish samples for one species were collected in each season. In Yen So Lake, only carp, mud carp, and hypophtalmichthys were collected rainy season; mud carp and hypophtalmichthys were collected in the dry season. In both seasons, twenty-four and fifteen fish samples were collected in West Lake and Yen So Lake, respectively. The bodyweights of fish samples were range from 0.6 to 2.6 kg. The collected fish samples were washed then cut into thin slice and ground well. Each 5g of fish sample was processed based on the UNU project document [17]. PFSAs were extracted, purified and concentrated using solid phase extraction techniques using weak anion exchange columns (WAX, Oasis). The final elution was filtered via 0.2 µm syringe filter before kept into a 1ml injection vial. 2.1.4. PFASs analysis PFASs were analyzed by LC-MS/MS 8040, Shimadzu, Japan. The LC system was equipped with a column (Poroshell 120, EC.C18 (2.1 mm I.D. × 150 mm L, 2.7 μm) and guard column EC-C18, Agilent, USA. The mobile phase consisted of a binary mixture of A (2 mM.L -1 ammonium acetate in water with methanol in a ratio of volume is 9 and 1) and solvent B (methanol) at flow rate of 0.25 ml.min -1 . The gradient, the start with 50% B in 2 min increased to 95% B for 18 min and linearly at 95% B for 4 min then ramped to Survey of perfluoroalkyl substances concentration and their bioaccumulation in fish 39 50%A for 5 min. Total running time was 29 min. The inject volume was 2μL. The MS system was running with an electrospray ionization source in negative mode (ESI) at 3.5kV. 2.1.5. Quality Assurance and Quality Control Mass-labeled 13 C of 7 pefluoroalkyl carboxylic acid compounds (including C4, C6, C8, C9, C10, C11, and C12) and marked 18 O, 13 C of 2 Perfluoroalkylsulfonate compounds (including C6 and C8) were used as internal standards for PFASs, being added to fish homogenates before digestion to minimize analytical bias. Procedural blanks were tested every 5 - 10 samples to check for possible laboratory contaminations and interferences. Matrix spike recovery was determined by spiking mixed target standards into the fish muscle samples, followed by the extraction and analysis. In a batch of samples on LC- MS/MS, the standard solution was checked for 10 replications. Quantitative limits for 12 PFASs ranged from 0.01 to 0.06 ng.g -1 for fish homogenates samples. The recovery of 12 PFASs ranged from 81% to 125% (CV 3-12%) for fish matrix. 2.2. Result and discussion 2.2.1. PFASs concentrations in fish samples The total of PFASs concentrations in the fish samples are presented in figure 2 for two lakes. PFASs were detected in all four fish species (catfish, mud carp, hypophtalmichthys, and carp) in both lakes. The PFASs concentration in fish muscle in Yen So lake tends to be higher than those in West Lake. In comparison with previous reports, the total concentration of PFASs in fish blood samples in Yen So lake was higher than those in West Lake [18]. This is explained by the fact that Yen So lake contains wastewater of Hanoi city from To Lich, Kim Nguu, Set and Lu rivers while the West Lake only contains domestic waste water from residential areas along the lake and rainwater from the surrounding area. Figure 2. PFASs concentrations in fish samples in West lake and Yen So lake The PFASs concentrations are different in four fish species and decrease from catfish, mud card, hypophtalmichthys to carp in West Lake. The PFASs concentration average was in range from 1.98 ng.g -1 w.w. in catfish to 0.44 ng.g -1 w.w in carp. The catfish N. T. Ngoc, P. T. L. Anh, P. D. Quang, T. T. Kim, T. T. Mai, D. H. Anh and P. H. Viet 40 samples have higher PFASs concentration because they live in the bottom water layer and sediment of the lake. Other while, their average body weight is the highest among other fish samples species. Although we only study the PFASs contamination on three fish species in Yen So Lake, but the PFASs contamination concentration are higher than those in West Lake. The PFASs concentrations decrease from hypophtalmichthys to carp, and mud card. 2.2.2. Composition profiles of various PFASs in fish samples Figure 3. Distribution of 12 analysed PFASs in fish muscle samples: (a) in West lake and (b) in Yen So lake The composition profiles of PFASs are presented in figure 3. Five perfluoroalkylcarboxylic acids (PFOA, PFNA, PFDA, PFUdA, and PFDoA) and only one perfloankylsulfonates compound (PFOS) were found in fish samples in both lakes. The concentrations were different in various compounds. Such as in catfish sample in West Lake, the concentrations were: PFOA (0.005 ng.g -1 w.w), PFNA (0.054 ng.g -1 w.w), PFDA (0.81 ng.g -1 w.w), PFUdA (0.66 ng.g -1 w.w), and PFDoA (0.33 ng.g -1 w.w). The PFASs with long-chain carbon compounds such as PFNA, PFDA, PFUdA and PFDoA were predominant in the entire both lakes. This may be explained by a more extensive use in consumer products in the country and/or by their relatively higher solubility and thus higher mobility in water [19]. The bioaccumulative of PFASs should be studied to find out the different concentration in various compounds. 2.2.3. Bio-Accumulation of fish The water environment can be significantly effective to aquatic biota. Fish is one of specific bio-indicators shows for water contamination level. Mean bioconcentration factors (BCF) were calculated based on PFASs concentration measured in water and biota collected from the same area, followed in equation 1. w f C C BCF  (1) where Cf is the PFASs concentration in fish (ng.g -1 w.w) and Cw is the PFASs concentration in water (ng.mL -1 ). Twenty surface water samples were collected in each study lake to calculate BCF. BCF values of fish samples are presented in the table 2. PFNA, PFDA, PFDoA and PFOS (a) (b) Survey of perfluoroalkyl substances concentration and their bioaccumulation in fish 41 were the main PFASs components bioaccumulated in fish samples in both lakes. The PFDoA‟s BCF values were the highest (854 - 3743), whereas PFOA‟s BFC values were the lowest in both lakes (2.19 - 27.5). In perfluoroalkylcarboxylic acids group, BFC values increase with the carbon chain length. This tendency is similar to other PFASs bioaccumulation studies [20, 21]. A. Hagenaars et al., found that PFASs with longer chain lengths are more toxic than PFASs with shorter chain lengths [22]. Comparison based on the functional groups of compounds with the same chain length indicates that PFASs with a sulfonate group have a larger toxic potential than the ones with a carboxyl group. In this study results, PFOS‟s BCF value was higher than PFOA‟s. Depend on individual living environment and fish species, PFOS‟s BFC values are 10 to 135 times more than PFOA‟s. Lam et al. also reported the BCF values for the longer carbon chain PFASs were higher than those for the shorter carbon chain PFASs in tilapia liver. The PFOA concentrations in water were relatively higher than those of PFOS, but the BCFs of PFOA in biota were less than those of PFOS [23]. Table 2. BCFs for individual PFASs P F B A P F P eA P F H x A P F H p A P F O A P F N A P F D A P F U d A P F D o A P F B S P F H x S P F O S West lake Catfish - - - - 2.19 132 1654 - 3044 - - 298 Mud carp - - - - 27.4 90.4 656 - 1943 - - 260 Hypo. - - - - - 18.6 543 - 1287 - - 269 Carp - - - - 5.78 92.4 172 - 854 - - 541 Yen So lake Mud carp - - - - 27.5 46.7 600 - 2515 - - 145 Hypo. - - - - - 37.2 1066 - 3367 - - 472 Carp - - - - - 20.6 659 - 3743 - - 671 “-“ non- detectable data 3. Conclusion The research results provide the valuable information of PFASs contamination in freshwater fish species of two urban lakes in Hanoi. The source of PFASs contamination in these lakes related to the wastewater from municipal discharge. Yen So lake reserves the municipal wastewater of Hanoi therefore the PFASs contamination concentrations are higher than those in West lake. Five PFCAs including PFOA, PFNA, PFDA, PFUdA, and PFDoA were found in fish muscle samples in both West Lake and Yen So Lake. Only PFOS dominated PFSAs N. T. Ngoc, P. T. L. Anh, P. D. Quang, T. T. Kim, T. T. Mai, D. H. Anh and P. H. Viet 42 compound was found. The BCF of PFDoA was the highest in both study lakes (854.48 - 3742.68), whereas PFOA‟s BFC values were the lowest in both lakes (2.19 - 27.48). In PFCAs acids group, BFC values increased with the carbon chain length but with the same carbon chain length, BCF value for PFOS were higher than for PFOA. PFASs are concerned contaminants in recently because of their bioaccumulation, toxicity, and availability. The further studies with greater numbers of water, sediments, and fish are needed for accurate assessment of sources and pathways of exposures, and bioaccumulation of PFASs in aquatic environment in other locations in Vietnam. Acknowledgements. The research was conducted in the frame of the project “Monitoring and Management of POPs in Asia” co-ordinate by the United Nation University and supported a part finance from Shimadzu Co., Japan. 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