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Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland
Chemosphere xxx (2014) xxx–xxx
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Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland Jani Koponen a,⇑, Riikka Airaksinen a, Anja Hallikainen b, Pekka J. Vuorinen c, Jaakko Mannio d, Hannu Kiviranta a a
National Institute for Health and Welfare, Department of Environmental Health, Kuopio, Finland Finnish Food Safety Authority Evira, Helsinki, Finland Finnish Game and Fisheries Research Institute, Helsinki, Finland d Finnish Environment Institute, Helsinki, Finland b c
h i g h l i g h t s Domestic Baltic and freshwater fish are a source of PFAAs in the Finnish diet. Total PFAA concentration in the Baltic and freshwater fishes varied from 0.31 to 46 ng g
1
fresh weight.
Farmed fish in Finland is not a significant dietary source of PFAA for humans. PFAA levels in a single fish species are not representative of the PFAA contamination in a given area.
a r t i c l e
i n f o
Article history: Received 29 March 2014 Received in revised form 14 August 2014 Accepted 26 August 2014 Available online xxxx Handling Editor: I. Cousins Keywords: Perfluoroalkyl acid Baltic fish PFOS Dietary source Finland
a b s t r a c t In this study, the concentration of perfluoroalkyl acids (PFAAs) in various edible Finnish Baltic Sea, freshwater, and farmed fish species were analysed. PFAAs were present in all the Baltic and freshwater species, but were not observed in any farmed fish. The most abundant compound in each species was perfluorooctane sulfonate (PFOS), comprising 41–100% of the total concentration. The total PFAA concentration varied considerably from 0.31 to 46 ng g 1 fresh weight. A notable variation in the PFAA concentrations implies that a single fish species alone is not suitable for monitoring PFAA contamination in a certain area. Our results confirm that wild domestic fish is one of the PFAA source in the Finnish diet. Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction Perfluoroalkyl acids (PFAAs), including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS), are a subgroup of per- and polyfluorinated alkyl substances (PFAS). These substances have been widely used in many industrial and commercial
Abbreviations: fw, fresh weight; LC–ESI–MS/MS, liquid chromatography electrospray tandem mass spectrometry; LOQ, limits of quantification; PFAA, perfluoroalkyl acid; PFAS, per- and polyfluorinated alkyl substances; PFOS, perfluorooctane sulfonic acid. ⇑ Corresponding author. Address: P.O. Box 95, FI-70701 Kuopio, Finland. Tel.: +358 29 524 6350; fax: +358 29 524 6499. E-mail address: jani.koponen@thl.fi (J. Koponen).
applications (Buck et al., 2011). Since the carbon–fluorine bond is extremely strong and stable some of these compounds are chemically and biologically inert. However, these properties are highly related to the molecular weight and number of C–F bonds of the compound (Buck et al., 2011). Although the PFAAs are persistent, a bioaccumulative potential of the compounds is highly dependent on a chain length of the fluorinated carbons, Perfluorinated carboxylates with seven fluorinated carbons or less are not bioaccumulative according to regulatory criteria (Conder et al., 2008). PFAAs are ubiquitous in the environment and present in both environmental and human matrices (Fromme et al., 2009). The use of PFOS has been limited in EU-legislation almost a decade ago (directive 2006/122/EC) and its use in water resistant consumer products will be reconsidered again in 2015.
http://dx.doi.org/10.1016/j.chemosphere.2014.08.077 0045-6535/Ó 2014 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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J. Koponen et al. / Chemosphere xxx (2014) xxx–xxx
Compounds in many classes of environmental pollutants have been associated with adverse health effects. PFAS may increase total and LDL cholesterol and the risk of breast cancer (Nelson et al., 2009; Steenland et al., 2009; Frisbee et al., 2010; Bonefeld-Jorgensen et al., 2011). Dietary intake is believed to be the major exposure route for PFAAs in the general adult population (Fromme et al., 2009; Haug et al., 2011; Vestergren et al., 2012). The Baltic Sea is highly susceptible to pollution because it is a closed sea area with little water exchange with the North Sea, and because of its large catchment area with a population of about 85 million people and a high number of pollutant sources. The environmental pollutant levels in Baltic fish are often higher than in larger water bodies such as the Atlantic and Pacific oceans (Burreau et al., 2006). In Baltic herring and salmon (Isosaari et al., 2006; Szlinder-Richert et al., 2009; Airaksinen et al., 2014), the levels of pollutants, such as dioxins and PCBs, occasionally exceed the legal maximum levels for fish set by EU (1258/2011). Fish and seafood have been found to be one of the major sources of human dietary exposure to PFAAs in the Nordic diet (Haug et al., 2010b; Vestergren et al., 2012). Yearly consumption of a domestic fish in Finland has been estimated to be 3.8 kg per person, including Baltic herring (0.3 kg), pike–perch (0.3 kg), perch (0.5 kg), whitefish (0.2 kg), vendace (0.6 kg) and farmed rainbow trout (1.0 kg) (FGFRI, 2012). The main objective of this study was to collect data about PFAA concentrations in fish commonly consumed in Finland for future dietary intake and human exposure assessments, and to investigate possible correlations between PFAA concentrations and selected physiological parameters in fish. In the future, this data can be utilized as a reference data for the measures taken in the follow up and monitoring of contaminated Baltic Sea fish.
fishing areas across the Finnish coast of the Baltic Sea (areas nearby the cities of Oulu, Pori, Turku, Hanko, and Kotka), Helsinki Vanhankaupunginlahti bay, a large freshwater Lake Päijänne, and four fish farming facilities (Fig. 1). Most of the individual samples were pooled. The pooled samples consisted of 2–10 individuals. Fish age was determined in scale or appropriate bony structure. The samples were frozen until preparation. From the large fish, a medallion was cut from around the dorsal fin and for small fish, the head was removed. Intestine and skin were removed, and meat and subcutaneous fat were homogenized to form a pooled sample according to EU directive 1883/2006. The homogenized fish samples were freeze-dried and stored frozen until PFAA analysis.
2. Materials and methods
2.3. PFAA analysis
2.1. Sampling and preparation
For quantitation prior to an extraction procedure a 2.5 ng of mass labelled internal standards in 50 lL of methanol were added into 0.3 g of freeze-dried fish samples. The samples were extracted twice with 2 mL of 20 mM ammonium acetate in methanol. After mixing for 10 min at 2500 rpm with Vibramax 110 (Schwabach, Germany), the samples were centrifuged with Eppendorf 5810 (Hamburg, Germany) at 2500 g for 10 min. The supernatants were collected. The extracts were evaporated to dryness under a nitrogen flow and reconstituted to 300 lL of 60% aqueous methanol. Prior to instrumental analysis, the samples were filtered with 0.2 lm syringe filter (Pall Life Sciences, Ann Arbor, MI). The PFAAs were analysed using liquid chromatography negative ion electrospray tandem mass spectrometry (LC–ESI–MS/MS). Details of the
The species collected from the Baltic Sea were Baltic herring (Clupea harengus), pike–perch (Sander lucioperca), perch (Perca fluviatilis), burbot (Lota lota), whitefish (Coregonus lavaretus), salmon (Salmo salar), and vendace (Coregonus albula). In addition, perch and pike– perch were collected from Helsinki Vanhankaupunginlahti bay, and perch was collected from Lake Päijänne. Farmed fish species included in this study were whitefish and rainbow trout (Oncorhynchus mykiss) (Table 1). The selection of fish species was mainly based on the significance of fish in the Finnish diet. Altogether 296 individual fish samples were collected in 2009–2010 from five commercially and recreationally important
2.2. Chemicals and reagents Methanol (HPLC grade) and ammonium acetate were obtained from J.T. Baker (Deventer, the Netherlands), and N-methylpiperidine from Sigma–Aldrich (St. Louis, MO, USA). All the native PFAAs, i.e. perfluorohexanoic acid (PFHxA), -heptanoic acid (PFHpA), -octanoic acid (PFOA), -nonanoic acid (PFNA), -decanoic acid (PFDA), -undecanoic acid (PFUnA), -dodecanoic acid (PFDoA), -tridecanoic acid (PFTrA), -tetradecanoic acid (PFTeA), -hexanesulfonate (PFHxS), -heptanesulfonate (PFHpS), -octanesulfonate (PFOS) and -decanesulfonate (PFDS) were acquired from Wellington Laboratories Inc (Guelph, Ontario, Canada). Isotope labelled PFAAs (abb. MPFAA) were used as internal standards. MPFOA (1,2,3,4-13C4), MPFNA (1,2,3,4,5-13C5), MPFUnA (1,2,3,4,5,6,7-13C7), MPFDoA (1,2-13C2), MPFHxS (18O2) and MPFOS (1,2,3,4-13C4) were obtained from Wellington Laboratories Inc. and MPFDA (1,2,3,4,5,6,7,8,9-13C9) was from CIL (Andover, MA, USA).
Table 1 Gender, length, weight, age, and fat percentage in Baltic, freshwater, and farmed fish. Fishing area
Species
Region
Gender
Length (cm)
Weight (g)
Age (year)
Fat (%)
Baltic Sea
Baltic herring (n = 58) Pike–perch (n = 30) Perch (n = 25) Burbot (n = 49) Whitefish (n = 27) Salmon (n = 44) Vendace (n = 20)
Pori Oulu, Oulu, Oulu, Oulu, Oulu, Oulu
Male, female Male, female Male, female Male, female Male, female Male, female Female
16–22 37–45 26–28 47–58 29–51 76–94 16–17
28–76 420–830 200–290 590–1430 240–1250 4740–9320 29–36
4.2–17 3.4–7.0 5.2–8.0 3.0–5.6 2.5–6.6 1.8–2.2 1.8–2.0
2.2–13 0.93–3.1 1.8–2.9 0.71–0.89 2.7–6.7 13–20 5.1–5.4
Vanhankaupunginlahti bay
Pike–perch (n = 6) Perch (n = 7)
Helsinki Helsinki
Female Male, female
31–51 17–22
230–1110 70–130
3.0–9.0 5.0–10
n/a n/a
Lake Päijänne
Perch (n = 10)
Päijänne
Male, female
20–25
87–190
8.0–10
1.2–1.8
Farmed fish
Whitefish (n = 10) Rainbow trout (n = 10)
Northern and Southern Finland Central and Southern Finland
Male, female Female
38–39 45–50
650–670 1280–1830
n/a n/a
21–23 17–18
Turku, Kotka Pori, Turku, Hanko, Pori, Turku, Hanko, Pori, Turku, Hanko, Pori, Turku, Hanko,
Kotka Kotka Kotka Kotka
n = Number of individual fishes. n/a Not analysed.
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
J. Koponen et al. / Chemosphere xxx (2014) xxx–xxx
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Fig. 1. Map of the sampling areas. The numbered points represent regions off the cities of (1) Oulu, (2) Pori, (3) Turku, (4) Hanko, and (5) Kotka in the Finnish coast of the Baltic Sea, as well as (6) Helsinki Vanhankaupunginlahti bay and (7) Lake Päijänne. The fish farming facilities are not shown on the map.
LC–ESI–MS/MS parameters and quantitation have been presented earlier (Koponen et al., 2013). Concentrations of PFAAs are reported as ng g 1 fresh weight (fw). Limits of quantification (LOQs) for PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFHxS and PFOS was 0.18–0.39 ng g 1, and for PFTrA, PFTeA and PFDS 0.33–0.65 ng g 1 fw. In each sample batch, a blank sample and an in-house fish control sample, treated exactly as the real fish samples, were determined. Level of the PFAAs in the blank sample was below the LOQ, so a subtraction from the results of the real samples was not necessary. PFAA-spiked, homogenized and freeze-dried rainbow trout was used as the in-house control sample for determining an inter-batch (day to day) precision of the analysis. Coefficient of variation (CV) for the inter-batch precision for PFAAs was 3.0–23%, which was considered acceptable. Recoveries of the spiked-PFAAs were 72–138%. 2.4. Statistical analysis A correlation between the total PFAA concentration and the physiological parameters (weight, age and fat percentage) of fish was evaluated using either Pearson’s or Spearman’s correlation coefficient. Kolmogorov–Smirnov test was used to evaluate a normality of the data. Values at p < 0.05 was considered statistically significant. 3. Results and discussion Seven different PFAAs were detected in the fish samples, namely PFOS, PFOA, PFNA, PFDA, PFUnA, PFDoA, and PFTrA (Table 2). The most abundant compound in all of the samples was PFOS, comprising 41–100% of the total concentration.
3.1. PFAAs in Baltic fish Total PFAA concentration in fish of the Baltic Sea varied from 0.31 to 10 ng g 1 fw (Table 2). Overall, the concentrations were of similar magnitude than those observed in the Swedish Baltic coast (Berger et al., 2009). The highest PFAA concentrations in single sample (pooled or individual fish sample) were found in Baltic herring and pike–perch, and the lowest in burbot and whitefish, which differed from the previous report (Berger et al., 2009). The highest median concentration was found in salmon and pike–perch, and the lowest in burbot and vendace. There was substantial variation in the concentrations between individuals among the same species. PFOS was the most abundant compound found in every sample comprising 48–100% of the total concentration as has been detected in Canadian fish species (Houde et al., 2006). PFNA was present in nearly all the samples, whereas PFOA, ubiquitous in the environment (Fromme et al., 2009), was detected only in some specimens of Baltic herring. Low concentration of PFDA, PFUnA and PFTrA was also detected in some species. The short chain PFHxA, PFHpA and PFHxS, as well as long chain PFDoA, PFTeA and PFDS were not present in any of the samples. Similar homologue pattern as in the present study has also been observed in previous studies (Berger et al., 2009; van Leeuwen et al., 2009; Noorlander et al., 2011; Domingo et al., 2012). The Baltic fish in this study were collected from five different sampling areas of the northern and southern Finnish coast of the Baltic Sea (Fig. 1). The total PFAA concentration in each fish species in the sampling areas are shown in Fig. 2. Baltic herring and vendace were collected only from one sampling area and therefore not included in the Fig. 2. There were differences in total PFAA concentrations both between species and between different sampling areas among same species. The results show that the lowest PFAA
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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J. Koponen et al. / Chemosphere xxx (2014) xxx–xxx
Table 2 Perfluoroalkyl acids (PFAAs) in Baltic, freshwater, and farmed fish. PFAA concentration (ng g
1
fresh weight)a,b
Fishing area
Species
PFOS
PFOA
PFNA
PFDA
PFUnA
PFDoA
PFTrA
Total (median)
Baltic Sea
Baltic herring (n = 58) Pike–perch (n = 30) Perch (n = 25) Burbot (n = 49) Whitefish (n = 27) Salmon (n = 44) Vendace (n = 20)
0.86–4.8 2.1–4.9 1.2–4.8 0.31–7.5 0.33–4.6 1.5–5.6 0.60–0.88
<0.21–1.8 <0.28 <0.21 <0.20 <0.26 <0.39 <0.23
<0.21–2.7 <0.28–0.35 <0.21–0.83 <0.20–1.5 <0.26–0.63 <0.39 0.35–0.36
<0.21–0.22 <0.28 <0.21–0.53 <0.20–0.60 <0.26 <0.39 <0.23–0.25
<0.21–0.44 <0.28–0.82 0.23–0.78 <0.20–1.5 <0.26 <0.39 <0.23
<0.21 <0.28 <0.21 <0.20 <0.26 <0.39 <0.23
<0.36 <0.47–0.86 <0.36–0.58 <0.33 <0.44 <0.65 <0.38
0.86–10 (1.7) 2.1–7.2 (2.6) 1.8–7.4 (1.9) 0.31–3.4 (1.3) 0.33–5.0 (1.5) 1.5–5.6 (3.2) 1.2–1.3 (1.2)
Vanhankaupunginlahti bay
Pike–perch (n = 6) Perch (n = 7)
1.5–6.6 16–39
<0.21 <0.23
<0.21–0.33 <0.23–0.24
<0.21 0.47–1.1
<0.21–0.54 1.6–3.4
<0.21 0.34–0.77
<0.36 0.63–1.7
1.5–7.5 (4.1) 20–46 (27)
Lake Päijänne
Perch (n = 10)
1.5–1.6
<0.18
<0.18
0.18–0.31
0.60–1.2
<0.18
0.66–1.2
3.5–3.7 (3.5)
Farmed fish
Whitefish (n = 10) Rainbow trout (n = 10)
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.62 <0.59
–c –c
n = Number of individual fishes. a If the analyte is not detected, the value is marked as
Fig. 2. Total PFAA concentration (ng g Sea.
1
1
. None of these analytes were detected in any of the samples.
fw) in pike–perch (PP), perch (P), burbot (B), whitefish (W), and salmon (S) in the five sampling areas in the Finnish coast of the Baltic
concentrations were found in fish collected off the coast of Hanko (burbot 0.31 ng g 1 fw, whitefish 0.34 ng g 1 fw). PFAA levels in pike–perch collected off the coast of Oulu (6.2 ng g 1 fw) and perch off Pori (7.4 ng g 1 fw) were higher than in the other sampling areas. In terms of the highest PFAA concentration single fish species was not dominant in all the fishing locations. Taken together, our results support previous findings that the PFAA concentrations and homologue pattern in fish are highly influenced by geographic area and the studied species, (Houde et al., 2006; Haug et al., 2010a), possibly due to differences in food webs and feeding habits (Berger et al., 2009), and local emission sources of these substances, including river estuaries. Our findings suggest that one sampling location is not representative of a larger sea area and that environmental PFAA contamination cannot necessarily be reliably monitored by a single fish species, as suggested before (Berger et al., 2009). As shown in Fig. 3 the weight of the fish correlated poorly with the total PFAA concentration in fish species. Our data shows that only an inverse correlation between the PFAA concentration and fresh weight in the whitefish (p < 0.05) was present, but no correlation was observed with the other fish species (p > 0.05). The results imply that no growth dilution of PFAA concentration does exist in studied fishes, expect in the whitefish. Since the correlation was only observed in one species, this indicates that the correlations are highly species-specific (may even be fishing area specific) and cannot be generalised for any fish species. Although the age and weight of the fish usually have strong correlation, no correlation between age and total PFAA concentration, not even with the whitefish, was observed (p > 0.05). In addition to the weight and age the role of fat content of the fish to the PFAA concentration was studied (Fig. 4). The correlation
between the fat content and the PFAA concentration was highly species-specific. For pike–perch (p < 0.05) and salmon (p < 0.01) a positive correlation was observed, whereas for whitefish the correlation was inverse (p < 0.05). Furthermore, no correlation was present for the Baltic herring, perch and burbot (p > 0.05). We note that the result may be affected by the fact that low the range of the fat content in some species was quite restricted. Since both the positive, inverse and no correlation were observed, the data indicates (as stated above) the correlations are highly species-specific and hence cannot be generalised for any fish species. 3.2. PFAAs in Helsinki Vanhankaupunginlahti bay and Lake Päijänne Total PFAA concentration in pike–perch and perch in Vanhankaupunginlahti bay varied from 1.5 to 7.5 ng g 1 and from 20 to 46 ng g 1 fw, respectively (Table 2). For pike–perch, the concentrations found in Vanhankaupunginlahti bay were at the same level as in the Baltic Sea sampling areas, located in the open sea. However, for perch, the concentrations were 4–15 times higher in Vanhankaupunginlahti bay than in the other coastal sea areas. Vanhankaupunginlahti bay area is a shallow, relatively closed bay with an inflow of the river Vantaa which runs through several major population centres in southern Finland. There has been and still is quite a lot of industry along the Vantaa river and their wastewater treatment plants together with numerous municipal wastewater treatment plants burden the river Vantaa and Vanhankaupunginlahti bay area with the organic contaminants although the water purification methods are state of the art level. The perch in the Vanhankaupunginlahti bay is a very local fish species, and is constantly exposed to higher levels of PFAAs as compared to the other areas in the Baltic Sea. The PFAA
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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Fig. 3. Species-specific relation between the total PFAA concentration and weight of the Baltic fish. The significant correlation coefficients (R) are indicated as ⁄, p < 0.05.
Fig. 4. Species-specific relation between the total PFAA concentration and fat content in the Baltic fish. The significant correlation coefficients (R) are indicated as ⁄, p < 0.05.
concentrations in perch in Vanhankaupunginlahti bay were relatively high as compared to previous reports from Nordic fish (Berger et al., 2009; Haug et al., 2010a; Vestergren et al., 2012), but is still multiple times lower than in fish from highly polluted water areas (Kannan et al., 2005). PFOS was the most abundant compound found in every sample, comprising 80–100% of the total concentration. Additionally the PFNA, PFDA, PFUnA, PFDoA and PFTrA were detected. The PFOA, the short chain PFHxA, PFHpA and PFHxS, as well as long chain PFTeA and PFDS were not present in any of the samples. Since perch is one of the most common fish caught in recreational fishery from freshwater areas in Finland, only this species was investigated in the present study. Total PFAA concentrations in perch in Lake Päijänne were 3.5–3.7 ng g 1 fw, which is at the same level as found in Kotka area of the Baltic Sea (3.7 ng g 1 fw). Compared to perch from the other sampling areas, the PFAA concentration in perch in Lake Päijänne was lower than in perch in Vanhankaupunginlahti bay (20–46 ng g 1 fw) and in Pori area of the Baltic Sea (7.4 ng g 1 fw), and higher than in Turku and Hanko area of the Baltic Sea (1.8–1.9 ng g 1 fw). The PFAA homologue pattern differed strongly between Lake Päijänne and the Baltic Sea perch (Table 2). Although the PFOS was still the main compound (41–44% of total PFAA), the relative concentration of the PFUnA and PFTrA was up to 33% and 34%, respectively. Additionally low concentration of PFDA were found in the perch, whereas the PFHxA, PFHpA PFOA, PFNA, PFDoA, PFTeA, PFHxS and PFDS were not detected. In agreement with the previous report (Berger et al., 2009), the variances in the PFAA profile between the sampling areas indicate different sources of contamination. Waste water and landfill effluents can be sources of PFAAs into the environment (Ahrens, 2011). Industrial and municipal waste waters and landfill effluents are most likely one of the major sources of PFAAs in Lake Päijänne, which may result in the differences in the PFAA profiles between this water area and the Baltic Sea. Additionally, as mentioned above, trophic level of the species
in the food web and differences in feeding habits may contribute to the accumulation pattern of PFAAs (Berger et al., 2009). 3.3. PFAAs in farmed fish Concentrations of all the analysed PFAAs in farmed whitefish and rainbow trout from four different fish farming facilities were below the LOQ (Table 2). This is in agreement with a previous study, where the reported concentrations were mostly below 0.1–0.2 ng g 1 fw (van Leeuwen et al., 2009). Furthermore we note that no growth dilution was observed, since the weight of the farmed fishes was not higher than that of the Baltic fish (Table 1). Our data implies that farmed fish in Finland are probably not a significant source of PFAA dietary exposure for humans. The current data shows that whitefish and salmon do not readily accumulate PFAAs through the farming environment and feeding. This underlines that PFAA-free environment and purity of the fish meal and feed are essential to minimize the PFAA exposure of the farmed fish. 4. Conclusions The PFAA contamination is demonstrated in both the Finnish Baltic Sea and freshwater fish. This confirms that a consumed domestic fish is a source of PFAAs in the Finnish diet. However, there is substantial variation in the PFAA concentrations both between species and between sampling locations. Therefore, based on the presented data, any fish consumption recommendations in order to avoid exposure to these substances would be quite challenging and further studies are needed in order to fill the existing data gaps. Our data, however, implies that farmed fish in Finland is not a significant source of PFAA for humans. The importance of the fish on the total PFAA intake and human exposure in Finnish population is still unclear, since lots of crucial data of the different PFAA sources is lacking and remains to be studied.
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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Our results suggest that PFAA levels in a single fish species are not representative of PFAA contamination in a given area. Environmental monitoring, including fish, is a valuable tool to reveal local point sources of contamination and analysing several PFAAs can help to find out the specific source of contamination. References Airaksinen, R., Hallikainen, A., Rantakokko, P., Ruokojärvi, P., Vuorinen, P.J., Parmanne, R., Verta, M., Mannio, J., Kiviranta, H., 2014. Time trends and congener profiles of PCDD/Fs, PCBs, and PBDEs in Baltic herring off the coast of Finland during 1978–2009. Chemosphere 114, 165–171. http://dx.doi.org/ 10.1016/j.chemosphere.2014.03.097. Ahrens, L., 2011. Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate. J. Environ. Monit. 13, 20. http://dx.doi.org/10.1039/ c0em00373e. Berger, U., Glynn, A., Holmström, K.E., Berglund, M., Ankarberg, E.H., Törnkvist, A., 2009. Fish consumption as a source of human exposure to perfluorinated alkyl substances in Sweden – analysis of edible fish from Lake Vättern and the Baltic Sea. Chemosphere 76, 799–804. http://dx.doi.org/10.1016/ j.chemosphere.2009.04.044. Bonefeld-Jorgensen, E.C., Long, M., Bossi, R., Ayotte, P., Asmund, G., Krüger, T., Ghisari, M., Mulvad, G., Kern, P., Nzulumiki, P., Dewailly, E., 2011. Perfluorinated compounds are related to breast cancer risk in greenlandic inuit: a case control study. Environ. Health 10, 88–103. http://dx.doi.org/10.1186/1476-069X-10-88. Buck, R.C., Franklin, J., Berger, U., Conder, J.M., Cousins, I.T., de Voogt, P., Jensen, A.A., Kannan, K., Mabury, S.A., van Leeuwen, S.P., 2011. Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integr. Environ. Assess. Manage. 7, 513–541. http://dx.doi.org/ 10.1002/ieam.258. Burreau, S., Zebühr, Y., Broman, D., Ishaq, R., 2006. Biomagnification of PBDEs and PCBs in food webs from the Baltic Sea and the northern Atlantic Ocean. Sci. Total Environ. 366, 659–672. http://dx.doi.org/10.1016/j.scitotenv.2006.02.005. Conder, J.M., Hoke, R.A., de Wolf, W., Russell, M.H., Buck, R.C., 2008. Are PFCAs bioaccumulative? A critical review and comparison with regulatory criteria and persistent lipophilic compounds. Environ. Sci. Technol. 42, 995–1003. http:// dx.doi.org/10.1021/es070895g. Domingo, J.L., Ericson-Jogsten, I., Perelló, G., Nadal, M., Van Bavel, B., Kärrman, A., 2012. Human exposure to perfluorinated compounds in Catalonia, Spain: contribution of drinking water and fish and shellfish. J. Agric. Food Chem. 60, 4408–4415. http://dx.doi.org/10.1021/jf300355c. FGFRI, 2012. Finnish fisheries statistics. Finnish Game and Fisheries Research Institute. Frisbee, S.J., Shankar, A., Knox, S.S., Steenland, K., Savitz, D.A., Fletcher, T., Ducatman, A.M., 2010. Perfluorooctanoic acid, perfluorooctanesulfonate, and serum lipids in children and adolescents: results from the C8 health project. Arch. Pediatr. Adolescent Med. 164, 860–869. http://dx.doi.org/10.1001/archpediatrics. 2010.163. Fromme, H., Tittlemier, S.A., Völkel, W., Wilhelm, M., Twardella, D., 2009. Perfluorinated compounds – exposure assessment for the general population
in western countries. Int. J. Hyg. Environ. Health 212, 239–270. http:// dx.doi.org/10.1016/j.ijheh.2008.04.007. Haug, L.S., Huber, S., Becher, G., Thomsen, C., 2011. Characterisation of human exposure pathways to perfluorinated compounds — comparing exposure estimates with biomarkers of exposure. Environ. Int. 37, 687–693. http:// dx.doi.org/10.1016/j.envint.2011.01.011. Haug, L.S., Salihovic, S., Jogsten, I.E., Thomsen, C., van Bavel, B., Lindström, G., Becher, G., 2010a. Levels in food and beverages and daily intake of perfluorinated compounds in Norway. Chemosphere 80, 1137–1143. http://dx.doi.org/ 10.1016/j.chemosphere.2010.06.023. Haug, L.S., Thomsen, C., Brantsæter, A.L., Kvalem, H.E., Haugen, M., Becher, G., Alexander, J., Meltzer, H.M., Knutsen, H.K., 2010b. Diet and particularly seafood are major sources of perfluorinated compounds in humans. Environ. Int. 36, 772–778. http://dx.doi.org/10.1016/j.envint.2010.05.016. Houde, M., Martin, J.W., Letcher, R.J., Solomon, K.R., Muir, D.C.G., 2006. Biological monitoring of polyfluoroalkyl substances: a review. Environ. Sci. Technol. 40, 3463–3473. http://dx.doi.org/10.1021/es052580b. Isosaari, P., Hallikainen, A., Kiviranta, H., Vuorinen, P.J., Parmanne, R., Koistinen, J., Vartiainen, T., 2006. Polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, naphthalenes and polybrominated diphenyl ethers in the edible fish caught from the Baltic Sea and lakes in Finland. Environ. Pollut. 141, 213– 225. http://dx.doi.org/10.1016/j.envpol.2005.08.055. Kannan, K., Tao, L., Sinclair, E., Pastva, S.D., Jude, D.J., Giesy, J.P., 2005. Perfluorinated compounds in aquatic organisms at various trophic levels in a Great Lakes food chain. Arch. Environ. Contam. Toxicol. 48, 559–566. http://dx.doi.org/10.1007/ s00244-004-0133-x. Koponen, J., Rantakokko, P., Airaksinen, R., Kiviranta, H., 2013. Determination of selected perfluorinated alkyl acids and persistent organic pollutants from a small volume human serum sample relevant for epidemiological studies. J. Chromatogr. A 1309, 48–55. http://dx.doi.org/10.1016/j.chroma.2013.07.064. Nelson, J.W., Hatch, E.E., Webster, T.F., 2009. Exposure to polyfluoroalkyl chemicals and cholesterol, body weight, and insulin resistance in the general U.S. Population. Environ. Health Perspect. 118, 197–202. http://dx.doi.org/ 10.1289/ehp.0901165. Noorlander, C.W., van Leeuwen, S.P.J., te Biesebeek, J.D., Mengelers, M.J.B., Zeilmaker, M.J., 2011. Levels of perfluorinated compounds in food and dietary intake of PFOS and PFOA in The Netherlands. J. Agric. Food Chem. 59, 7496– 7505. http://dx.doi.org/10.1021/jf104943p. Steenland, K., Tinker, S., Frisbee, S., Ducatman, A., Vaccarino, V., 2009. Association of perfluorooctanoic acid and perfluorooctane sulfonate with serum lipids among adults living near a chemical plant. Am. J. Epidemiol. 170, 1268–1278. http:// dx.doi.org/10.1093/aje/kwp279. Szlinder-Richert, J., Barska, I., Usydus, Z., Ruczyn´ska, W., Grabic, R., 2009. Investigation of PCDD/Fs and dl-PCBs in fish from the southern Baltic Sea during the 2002–2006 period. Chemosphere 74, 1509–1515. http://dx.doi.org/ 10.1016/j.chemosphere.2008.11.038. Van Leeuwen, S.P.J., van Velzen, M.J.M., Swart, C.P., van der Veen, I., Traag, W.A., de Boer, J., 2009. Halogenated contaminants in farmed salmon, trout, tilapia, pangasius, and shrimp. Environ. Sci. Technol. 43, 4009–4015. http://dx.doi.org/ 10.1021/es803558r. Vestergren, R., Berger, U., Glynn, A., Cousins, I.T., 2012. Dietary exposure to perfluoroalkyl acids for the Swedish population in 1999, 2005 and 2010. Environ. Int. 49, 120–127. http://dx.doi.org/10.1016/j.envint.2012.08.016.
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland Jani Koponen a,⇑, Riikka Airaksinen a, Anja Hallikainen b, Pekka J. Vuorinen c, Jaakko Mannio d, Hannu Kiviranta a a
National Institute for Health and Welfare, Department of Environmental Health, Kuopio, Finland Finnish Food Safety Authority Evira, Helsinki, Finland Finnish Game and Fisheries Research Institute, Helsinki, Finland d Finnish Environment Institute, Helsinki, Finland b c
h i g h l i g h t s Domestic Baltic and freshwater fish are a source of PFAAs in the Finnish diet. Total PFAA concentration in the Baltic and freshwater fishes varied from 0.31 to 46 ng g
1
fresh weight.
Farmed fish in Finland is not a significant dietary source of PFAA for humans. PFAA levels in a single fish species are not representative of the PFAA contamination in a given area.
a r t i c l e
i n f o
Article history: Received 29 March 2014 Received in revised form 14 August 2014 Accepted 26 August 2014 Available online xxxx Handling Editor: I. Cousins Keywords: Perfluoroalkyl acid Baltic fish PFOS Dietary source Finland
a b s t r a c t In this study, the concentration of perfluoroalkyl acids (PFAAs) in various edible Finnish Baltic Sea, freshwater, and farmed fish species were analysed. PFAAs were present in all the Baltic and freshwater species, but were not observed in any farmed fish. The most abundant compound in each species was perfluorooctane sulfonate (PFOS), comprising 41–100% of the total concentration. The total PFAA concentration varied considerably from 0.31 to 46 ng g 1 fresh weight. A notable variation in the PFAA concentrations implies that a single fish species alone is not suitable for monitoring PFAA contamination in a certain area. Our results confirm that wild domestic fish is one of the PFAA source in the Finnish diet. Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction Perfluoroalkyl acids (PFAAs), including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS), are a subgroup of per- and polyfluorinated alkyl substances (PFAS). These substances have been widely used in many industrial and commercial
Abbreviations: fw, fresh weight; LC–ESI–MS/MS, liquid chromatography electrospray tandem mass spectrometry; LOQ, limits of quantification; PFAA, perfluoroalkyl acid; PFAS, per- and polyfluorinated alkyl substances; PFOS, perfluorooctane sulfonic acid. ⇑ Corresponding author. Address: P.O. Box 95, FI-70701 Kuopio, Finland. Tel.: +358 29 524 6350; fax: +358 29 524 6499. E-mail address: jani.koponen@thl.fi (J. Koponen).
applications (Buck et al., 2011). Since the carbon–fluorine bond is extremely strong and stable some of these compounds are chemically and biologically inert. However, these properties are highly related to the molecular weight and number of C–F bonds of the compound (Buck et al., 2011). Although the PFAAs are persistent, a bioaccumulative potential of the compounds is highly dependent on a chain length of the fluorinated carbons, Perfluorinated carboxylates with seven fluorinated carbons or less are not bioaccumulative according to regulatory criteria (Conder et al., 2008). PFAAs are ubiquitous in the environment and present in both environmental and human matrices (Fromme et al., 2009). The use of PFOS has been limited in EU-legislation almost a decade ago (directive 2006/122/EC) and its use in water resistant consumer products will be reconsidered again in 2015.
http://dx.doi.org/10.1016/j.chemosphere.2014.08.077 0045-6535/Ó 2014 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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Compounds in many classes of environmental pollutants have been associated with adverse health effects. PFAS may increase total and LDL cholesterol and the risk of breast cancer (Nelson et al., 2009; Steenland et al., 2009; Frisbee et al., 2010; Bonefeld-Jorgensen et al., 2011). Dietary intake is believed to be the major exposure route for PFAAs in the general adult population (Fromme et al., 2009; Haug et al., 2011; Vestergren et al., 2012). The Baltic Sea is highly susceptible to pollution because it is a closed sea area with little water exchange with the North Sea, and because of its large catchment area with a population of about 85 million people and a high number of pollutant sources. The environmental pollutant levels in Baltic fish are often higher than in larger water bodies such as the Atlantic and Pacific oceans (Burreau et al., 2006). In Baltic herring and salmon (Isosaari et al., 2006; Szlinder-Richert et al., 2009; Airaksinen et al., 2014), the levels of pollutants, such as dioxins and PCBs, occasionally exceed the legal maximum levels for fish set by EU (1258/2011). Fish and seafood have been found to be one of the major sources of human dietary exposure to PFAAs in the Nordic diet (Haug et al., 2010b; Vestergren et al., 2012). Yearly consumption of a domestic fish in Finland has been estimated to be 3.8 kg per person, including Baltic herring (0.3 kg), pike–perch (0.3 kg), perch (0.5 kg), whitefish (0.2 kg), vendace (0.6 kg) and farmed rainbow trout (1.0 kg) (FGFRI, 2012). The main objective of this study was to collect data about PFAA concentrations in fish commonly consumed in Finland for future dietary intake and human exposure assessments, and to investigate possible correlations between PFAA concentrations and selected physiological parameters in fish. In the future, this data can be utilized as a reference data for the measures taken in the follow up and monitoring of contaminated Baltic Sea fish.
fishing areas across the Finnish coast of the Baltic Sea (areas nearby the cities of Oulu, Pori, Turku, Hanko, and Kotka), Helsinki Vanhankaupunginlahti bay, a large freshwater Lake Päijänne, and four fish farming facilities (Fig. 1). Most of the individual samples were pooled. The pooled samples consisted of 2–10 individuals. Fish age was determined in scale or appropriate bony structure. The samples were frozen until preparation. From the large fish, a medallion was cut from around the dorsal fin and for small fish, the head was removed. Intestine and skin were removed, and meat and subcutaneous fat were homogenized to form a pooled sample according to EU directive 1883/2006. The homogenized fish samples were freeze-dried and stored frozen until PFAA analysis.
2. Materials and methods
2.3. PFAA analysis
2.1. Sampling and preparation
For quantitation prior to an extraction procedure a 2.5 ng of mass labelled internal standards in 50 lL of methanol were added into 0.3 g of freeze-dried fish samples. The samples were extracted twice with 2 mL of 20 mM ammonium acetate in methanol. After mixing for 10 min at 2500 rpm with Vibramax 110 (Schwabach, Germany), the samples were centrifuged with Eppendorf 5810 (Hamburg, Germany) at 2500 g for 10 min. The supernatants were collected. The extracts were evaporated to dryness under a nitrogen flow and reconstituted to 300 lL of 60% aqueous methanol. Prior to instrumental analysis, the samples were filtered with 0.2 lm syringe filter (Pall Life Sciences, Ann Arbor, MI). The PFAAs were analysed using liquid chromatography negative ion electrospray tandem mass spectrometry (LC–ESI–MS/MS). Details of the
The species collected from the Baltic Sea were Baltic herring (Clupea harengus), pike–perch (Sander lucioperca), perch (Perca fluviatilis), burbot (Lota lota), whitefish (Coregonus lavaretus), salmon (Salmo salar), and vendace (Coregonus albula). In addition, perch and pike– perch were collected from Helsinki Vanhankaupunginlahti bay, and perch was collected from Lake Päijänne. Farmed fish species included in this study were whitefish and rainbow trout (Oncorhynchus mykiss) (Table 1). The selection of fish species was mainly based on the significance of fish in the Finnish diet. Altogether 296 individual fish samples were collected in 2009–2010 from five commercially and recreationally important
2.2. Chemicals and reagents Methanol (HPLC grade) and ammonium acetate were obtained from J.T. Baker (Deventer, the Netherlands), and N-methylpiperidine from Sigma–Aldrich (St. Louis, MO, USA). All the native PFAAs, i.e. perfluorohexanoic acid (PFHxA), -heptanoic acid (PFHpA), -octanoic acid (PFOA), -nonanoic acid (PFNA), -decanoic acid (PFDA), -undecanoic acid (PFUnA), -dodecanoic acid (PFDoA), -tridecanoic acid (PFTrA), -tetradecanoic acid (PFTeA), -hexanesulfonate (PFHxS), -heptanesulfonate (PFHpS), -octanesulfonate (PFOS) and -decanesulfonate (PFDS) were acquired from Wellington Laboratories Inc (Guelph, Ontario, Canada). Isotope labelled PFAAs (abb. MPFAA) were used as internal standards. MPFOA (1,2,3,4-13C4), MPFNA (1,2,3,4,5-13C5), MPFUnA (1,2,3,4,5,6,7-13C7), MPFDoA (1,2-13C2), MPFHxS (18O2) and MPFOS (1,2,3,4-13C4) were obtained from Wellington Laboratories Inc. and MPFDA (1,2,3,4,5,6,7,8,9-13C9) was from CIL (Andover, MA, USA).
Table 1 Gender, length, weight, age, and fat percentage in Baltic, freshwater, and farmed fish. Fishing area
Species
Region
Gender
Length (cm)
Weight (g)
Age (year)
Fat (%)
Baltic Sea
Baltic herring (n = 58) Pike–perch (n = 30) Perch (n = 25) Burbot (n = 49) Whitefish (n = 27) Salmon (n = 44) Vendace (n = 20)
Pori Oulu, Oulu, Oulu, Oulu, Oulu, Oulu
Male, female Male, female Male, female Male, female Male, female Male, female Female
16–22 37–45 26–28 47–58 29–51 76–94 16–17
28–76 420–830 200–290 590–1430 240–1250 4740–9320 29–36
4.2–17 3.4–7.0 5.2–8.0 3.0–5.6 2.5–6.6 1.8–2.2 1.8–2.0
2.2–13 0.93–3.1 1.8–2.9 0.71–0.89 2.7–6.7 13–20 5.1–5.4
Vanhankaupunginlahti bay
Pike–perch (n = 6) Perch (n = 7)
Helsinki Helsinki
Female Male, female
31–51 17–22
230–1110 70–130
3.0–9.0 5.0–10
n/a n/a
Lake Päijänne
Perch (n = 10)
Päijänne
Male, female
20–25
87–190
8.0–10
1.2–1.8
Farmed fish
Whitefish (n = 10) Rainbow trout (n = 10)
Northern and Southern Finland Central and Southern Finland
Male, female Female
38–39 45–50
650–670 1280–1830
n/a n/a
21–23 17–18
Turku, Kotka Pori, Turku, Hanko, Pori, Turku, Hanko, Pori, Turku, Hanko, Pori, Turku, Hanko,
Kotka Kotka Kotka Kotka
n = Number of individual fishes. n/a Not analysed.
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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3
Fig. 1. Map of the sampling areas. The numbered points represent regions off the cities of (1) Oulu, (2) Pori, (3) Turku, (4) Hanko, and (5) Kotka in the Finnish coast of the Baltic Sea, as well as (6) Helsinki Vanhankaupunginlahti bay and (7) Lake Päijänne. The fish farming facilities are not shown on the map.
LC–ESI–MS/MS parameters and quantitation have been presented earlier (Koponen et al., 2013). Concentrations of PFAAs are reported as ng g 1 fresh weight (fw). Limits of quantification (LOQs) for PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFHxS and PFOS was 0.18–0.39 ng g 1, and for PFTrA, PFTeA and PFDS 0.33–0.65 ng g 1 fw. In each sample batch, a blank sample and an in-house fish control sample, treated exactly as the real fish samples, were determined. Level of the PFAAs in the blank sample was below the LOQ, so a subtraction from the results of the real samples was not necessary. PFAA-spiked, homogenized and freeze-dried rainbow trout was used as the in-house control sample for determining an inter-batch (day to day) precision of the analysis. Coefficient of variation (CV) for the inter-batch precision for PFAAs was 3.0–23%, which was considered acceptable. Recoveries of the spiked-PFAAs were 72–138%. 2.4. Statistical analysis A correlation between the total PFAA concentration and the physiological parameters (weight, age and fat percentage) of fish was evaluated using either Pearson’s or Spearman’s correlation coefficient. Kolmogorov–Smirnov test was used to evaluate a normality of the data. Values at p < 0.05 was considered statistically significant. 3. Results and discussion Seven different PFAAs were detected in the fish samples, namely PFOS, PFOA, PFNA, PFDA, PFUnA, PFDoA, and PFTrA (Table 2). The most abundant compound in all of the samples was PFOS, comprising 41–100% of the total concentration.
3.1. PFAAs in Baltic fish Total PFAA concentration in fish of the Baltic Sea varied from 0.31 to 10 ng g 1 fw (Table 2). Overall, the concentrations were of similar magnitude than those observed in the Swedish Baltic coast (Berger et al., 2009). The highest PFAA concentrations in single sample (pooled or individual fish sample) were found in Baltic herring and pike–perch, and the lowest in burbot and whitefish, which differed from the previous report (Berger et al., 2009). The highest median concentration was found in salmon and pike–perch, and the lowest in burbot and vendace. There was substantial variation in the concentrations between individuals among the same species. PFOS was the most abundant compound found in every sample comprising 48–100% of the total concentration as has been detected in Canadian fish species (Houde et al., 2006). PFNA was present in nearly all the samples, whereas PFOA, ubiquitous in the environment (Fromme et al., 2009), was detected only in some specimens of Baltic herring. Low concentration of PFDA, PFUnA and PFTrA was also detected in some species. The short chain PFHxA, PFHpA and PFHxS, as well as long chain PFDoA, PFTeA and PFDS were not present in any of the samples. Similar homologue pattern as in the present study has also been observed in previous studies (Berger et al., 2009; van Leeuwen et al., 2009; Noorlander et al., 2011; Domingo et al., 2012). The Baltic fish in this study were collected from five different sampling areas of the northern and southern Finnish coast of the Baltic Sea (Fig. 1). The total PFAA concentration in each fish species in the sampling areas are shown in Fig. 2. Baltic herring and vendace were collected only from one sampling area and therefore not included in the Fig. 2. There were differences in total PFAA concentrations both between species and between different sampling areas among same species. The results show that the lowest PFAA
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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Table 2 Perfluoroalkyl acids (PFAAs) in Baltic, freshwater, and farmed fish. PFAA concentration (ng g
1
fresh weight)a,b
Fishing area
Species
PFOS
PFOA
PFNA
PFDA
PFUnA
PFDoA
PFTrA
Total (median)
Baltic Sea
Baltic herring (n = 58) Pike–perch (n = 30) Perch (n = 25) Burbot (n = 49) Whitefish (n = 27) Salmon (n = 44) Vendace (n = 20)
0.86–4.8 2.1–4.9 1.2–4.8 0.31–7.5 0.33–4.6 1.5–5.6 0.60–0.88
<0.21–1.8 <0.28 <0.21 <0.20 <0.26 <0.39 <0.23
<0.21–2.7 <0.28–0.35 <0.21–0.83 <0.20–1.5 <0.26–0.63 <0.39 0.35–0.36
<0.21–0.22 <0.28 <0.21–0.53 <0.20–0.60 <0.26 <0.39 <0.23–0.25
<0.21–0.44 <0.28–0.82 0.23–0.78 <0.20–1.5 <0.26 <0.39 <0.23
<0.21 <0.28 <0.21 <0.20 <0.26 <0.39 <0.23
<0.36 <0.47–0.86 <0.36–0.58 <0.33 <0.44 <0.65 <0.38
0.86–10 (1.7) 2.1–7.2 (2.6) 1.8–7.4 (1.9) 0.31–3.4 (1.3) 0.33–5.0 (1.5) 1.5–5.6 (3.2) 1.2–1.3 (1.2)
Vanhankaupunginlahti bay
Pike–perch (n = 6) Perch (n = 7)
1.5–6.6 16–39
<0.21 <0.23
<0.21–0.33 <0.23–0.24
<0.21 0.47–1.1
<0.21–0.54 1.6–3.4
<0.21 0.34–0.77
<0.36 0.63–1.7
1.5–7.5 (4.1) 20–46 (27)
Lake Päijänne
Perch (n = 10)
1.5–1.6
<0.18
<0.18
0.18–0.31
0.60–1.2
<0.18
0.66–1.2
3.5–3.7 (3.5)
Farmed fish
Whitefish (n = 10) Rainbow trout (n = 10)
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.37 <0.35
<0.62 <0.59
–c –c
n = Number of individual fishes. a If the analyte is not detected, the value is marked as
Fig. 2. Total PFAA concentration (ng g Sea.
1
1
. None of these analytes were detected in any of the samples.
fw) in pike–perch (PP), perch (P), burbot (B), whitefish (W), and salmon (S) in the five sampling areas in the Finnish coast of the Baltic
concentrations were found in fish collected off the coast of Hanko (burbot 0.31 ng g 1 fw, whitefish 0.34 ng g 1 fw). PFAA levels in pike–perch collected off the coast of Oulu (6.2 ng g 1 fw) and perch off Pori (7.4 ng g 1 fw) were higher than in the other sampling areas. In terms of the highest PFAA concentration single fish species was not dominant in all the fishing locations. Taken together, our results support previous findings that the PFAA concentrations and homologue pattern in fish are highly influenced by geographic area and the studied species, (Houde et al., 2006; Haug et al., 2010a), possibly due to differences in food webs and feeding habits (Berger et al., 2009), and local emission sources of these substances, including river estuaries. Our findings suggest that one sampling location is not representative of a larger sea area and that environmental PFAA contamination cannot necessarily be reliably monitored by a single fish species, as suggested before (Berger et al., 2009). As shown in Fig. 3 the weight of the fish correlated poorly with the total PFAA concentration in fish species. Our data shows that only an inverse correlation between the PFAA concentration and fresh weight in the whitefish (p < 0.05) was present, but no correlation was observed with the other fish species (p > 0.05). The results imply that no growth dilution of PFAA concentration does exist in studied fishes, expect in the whitefish. Since the correlation was only observed in one species, this indicates that the correlations are highly species-specific (may even be fishing area specific) and cannot be generalised for any fish species. Although the age and weight of the fish usually have strong correlation, no correlation between age and total PFAA concentration, not even with the whitefish, was observed (p > 0.05). In addition to the weight and age the role of fat content of the fish to the PFAA concentration was studied (Fig. 4). The correlation
between the fat content and the PFAA concentration was highly species-specific. For pike–perch (p < 0.05) and salmon (p < 0.01) a positive correlation was observed, whereas for whitefish the correlation was inverse (p < 0.05). Furthermore, no correlation was present for the Baltic herring, perch and burbot (p > 0.05). We note that the result may be affected by the fact that low the range of the fat content in some species was quite restricted. Since both the positive, inverse and no correlation were observed, the data indicates (as stated above) the correlations are highly species-specific and hence cannot be generalised for any fish species. 3.2. PFAAs in Helsinki Vanhankaupunginlahti bay and Lake Päijänne Total PFAA concentration in pike–perch and perch in Vanhankaupunginlahti bay varied from 1.5 to 7.5 ng g 1 and from 20 to 46 ng g 1 fw, respectively (Table 2). For pike–perch, the concentrations found in Vanhankaupunginlahti bay were at the same level as in the Baltic Sea sampling areas, located in the open sea. However, for perch, the concentrations were 4–15 times higher in Vanhankaupunginlahti bay than in the other coastal sea areas. Vanhankaupunginlahti bay area is a shallow, relatively closed bay with an inflow of the river Vantaa which runs through several major population centres in southern Finland. There has been and still is quite a lot of industry along the Vantaa river and their wastewater treatment plants together with numerous municipal wastewater treatment plants burden the river Vantaa and Vanhankaupunginlahti bay area with the organic contaminants although the water purification methods are state of the art level. The perch in the Vanhankaupunginlahti bay is a very local fish species, and is constantly exposed to higher levels of PFAAs as compared to the other areas in the Baltic Sea. The PFAA
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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Fig. 3. Species-specific relation between the total PFAA concentration and weight of the Baltic fish. The significant correlation coefficients (R) are indicated as ⁄, p < 0.05.
Fig. 4. Species-specific relation between the total PFAA concentration and fat content in the Baltic fish. The significant correlation coefficients (R) are indicated as ⁄, p < 0.05.
concentrations in perch in Vanhankaupunginlahti bay were relatively high as compared to previous reports from Nordic fish (Berger et al., 2009; Haug et al., 2010a; Vestergren et al., 2012), but is still multiple times lower than in fish from highly polluted water areas (Kannan et al., 2005). PFOS was the most abundant compound found in every sample, comprising 80–100% of the total concentration. Additionally the PFNA, PFDA, PFUnA, PFDoA and PFTrA were detected. The PFOA, the short chain PFHxA, PFHpA and PFHxS, as well as long chain PFTeA and PFDS were not present in any of the samples. Since perch is one of the most common fish caught in recreational fishery from freshwater areas in Finland, only this species was investigated in the present study. Total PFAA concentrations in perch in Lake Päijänne were 3.5–3.7 ng g 1 fw, which is at the same level as found in Kotka area of the Baltic Sea (3.7 ng g 1 fw). Compared to perch from the other sampling areas, the PFAA concentration in perch in Lake Päijänne was lower than in perch in Vanhankaupunginlahti bay (20–46 ng g 1 fw) and in Pori area of the Baltic Sea (7.4 ng g 1 fw), and higher than in Turku and Hanko area of the Baltic Sea (1.8–1.9 ng g 1 fw). The PFAA homologue pattern differed strongly between Lake Päijänne and the Baltic Sea perch (Table 2). Although the PFOS was still the main compound (41–44% of total PFAA), the relative concentration of the PFUnA and PFTrA was up to 33% and 34%, respectively. Additionally low concentration of PFDA were found in the perch, whereas the PFHxA, PFHpA PFOA, PFNA, PFDoA, PFTeA, PFHxS and PFDS were not detected. In agreement with the previous report (Berger et al., 2009), the variances in the PFAA profile between the sampling areas indicate different sources of contamination. Waste water and landfill effluents can be sources of PFAAs into the environment (Ahrens, 2011). Industrial and municipal waste waters and landfill effluents are most likely one of the major sources of PFAAs in Lake Päijänne, which may result in the differences in the PFAA profiles between this water area and the Baltic Sea. Additionally, as mentioned above, trophic level of the species
in the food web and differences in feeding habits may contribute to the accumulation pattern of PFAAs (Berger et al., 2009). 3.3. PFAAs in farmed fish Concentrations of all the analysed PFAAs in farmed whitefish and rainbow trout from four different fish farming facilities were below the LOQ (Table 2). This is in agreement with a previous study, where the reported concentrations were mostly below 0.1–0.2 ng g 1 fw (van Leeuwen et al., 2009). Furthermore we note that no growth dilution was observed, since the weight of the farmed fishes was not higher than that of the Baltic fish (Table 1). Our data implies that farmed fish in Finland are probably not a significant source of PFAA dietary exposure for humans. The current data shows that whitefish and salmon do not readily accumulate PFAAs through the farming environment and feeding. This underlines that PFAA-free environment and purity of the fish meal and feed are essential to minimize the PFAA exposure of the farmed fish. 4. Conclusions The PFAA contamination is demonstrated in both the Finnish Baltic Sea and freshwater fish. This confirms that a consumed domestic fish is a source of PFAAs in the Finnish diet. However, there is substantial variation in the PFAA concentrations both between species and between sampling locations. Therefore, based on the presented data, any fish consumption recommendations in order to avoid exposure to these substances would be quite challenging and further studies are needed in order to fill the existing data gaps. Our data, however, implies that farmed fish in Finland is not a significant source of PFAA for humans. The importance of the fish on the total PFAA intake and human exposure in Finnish population is still unclear, since lots of crucial data of the different PFAA sources is lacking and remains to be studied.
Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077
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Please cite this article in press as: Koponen, J., et al. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.08.077