Persistent organic pollutants in selected fishes of the ...

MARSYS-02884; No of Pages 5 Journal of Marine Systems xxx (2016) xxx–xxx

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Persistent organic pollutants in selected fishes of the Gulf of Finland Leili Järv a,⁎, Hannu Kiviranta b, Jani Koponen b, Panu Rantakokko b, Päivi Ruokojärvi b, Maia Radin d, Tiit Raid a, Ott Roots c, Mart Simm a a

Estonian Marine Institute of Tartu University, Mäealuse 14, 12618 Tallinn, Estonia National Institute for Health and Welfare, Neulaniementie 4, FI-70701 Kuopio, Finland Estonian Environmental Research Centre, Marja 4d, 10617 Tallinn, Estonia d Ministries of Rural Affairs of the Republic of Estonia, Lai 39/Lai 41, 15056 Tallinn, Estonia b c

a r t i c l e

i n f o

Article history: Received 28 March 2016 Received in revised form 27 September 2016 Accepted 2 October 2016 Available online xxxx Keywords: Polychlorinated biphenyls Perfluorinated compounds Polybrominated diphenyl ethers Organotin compounds Fish Gulf of Finland Baltic Sea

a b s t r a c t Fish samples of Baltic herring, sprat, flounder, perch, salmon, and river lamprey were collected from the Gulf of Finland in 2013 and 2014 with the aim to get an overview of the occurrence of pollutants in fish caught in Estonian waters. The content of non-dioxin-like polychlorinated biphenyls (ndl PCBs), polybrominated diphenyl ethers (PBDEs), organic tin (OT) and perfluorocompounds (PFAS) are examined and discussed in the study. The results revealed that potentially higher content of organo-tin compounds, perfluorocompounds and polybrominated diphenyl ethers in Baltic herring, salmon and river lamprey may cause concern regarding human exposure. It is important to link pollutant content to lipid content of fish taking into account their seasonal variation in different age classes. © 2016 Elsevier B.V. All rights reserved.

1. Introduction The Baltic Sea is a complex ecosystem with a multitude of physical, chemical and biological interactions functioning on various temporal and spatial scales. The environmental state of the Baltic Sea is influenced by both natural and anthropogenic factors. The key environmental stressors are (1) eutrophication, (2) over-fishing, (3) risk of chemical and/or oil spills, (4) marine litter, (5) invasive species and (6) hazardous substances. These environmental problems together with climate changes downscale the Baltic Sea's ability to provide ecosystem goods and services. The changes in the ecosystem state can have impacts also to human welfare. Hazardous substances, both natural and artificial compounds, cause adverse effects on the ecosystem. Examples are persistent organic pollutants (POPs) - PCB, DDT, dioxins, etc., which can be toxic even in very low concentrations, and also trace metals - mercury, lead, cadmium, etc., which are toxic in much higher concentrations generally. Pollution with the hazardous substances constitutes a serious threat to the Baltic Sea environment and has already led to detrimental effects

⁎ Corresponding author. E-mail addresses: [email protected] (L. Järv), Hannu.Kiviranta@thl.fi (H. Kiviranta), jani.koponen@thl.fi (J. Koponen), panu.rantakokko@thl.fi (P. Rantakokko), paivi.ruokojarvi@thl.fi (P. Ruokojärvi), [email protected] (M. Radin), [email protected] (T. Raid), [email protected] (O. Roots), [email protected] (M. Simm).

on biodiversity harming flora's and fauna's immune- and hormone systems impairing their general health and reproduction status. While some of hazardous substances bio-accumulating properties they magnify through the food chain to higher species at higher trophic levels posing a threat also for humans who consume fish caught in the Baltic Sea. The long residence time of hazardous substances, in combination with the introduction of new compounds, poses a grave threat for the state of the future Baltic Sea and health of future generations. (Bignert et al., 1998; HELCOM, 2010a, 2010b, 2010c). However, regardless to the actuality of the issue, the research of hazardous substances in the Baltic Sea (incl. the Gulf of Finland) environment has a fairly short history. Presently one of the four segments of the ecosystem health targeted by the HELCOM BSAP (Baltic Sea Action Plan) is monitoring of hazardous substances, with an ambitious zeroemission target for all manmade hazardous substances in the whole Baltic Sea catchment by 2021 (HELCOM, 2010c). The objectives of current study were: 1. to get a short overview of the content of selected persistent organic pollutants: non-dioxin-like polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organotin (OT) and perfluorinated compounds (PFC), in five most consumable fish species: Baltic herring, sprat, flounder, perch and highly profitable species salmon and river lamprey, of the Gulf of Finland, Baltic Sea. 2. to link the pollutant content to lipid content of fish and follow their seasonal variation in different age classes.

http://dx.doi.org/10.1016/j.jmarsys.2016.10.002 0924-7963/© 2016 Elsevier B.V. All rights reserved.

Please cite this article as: Järv, L., et al., Persistent organic pollutants in selected fishes of the Gulf of Finland, J. Mar. Syst. (2016), http://dx.doi.org/ 10.1016/j.jmarsys.2016.10.002

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L. Järv et al. / Journal of Marine Systems xxx (2016) xxx–xxx

3. to collect information as the basis for potential negotiation with EU about some specific clauses for the maximum allowable concentration values. 2. Material and methods 2.1. Study area The Gulf of Finland (Fig. 1) is located in the north-eastern part of the Baltic Sea and is the easternmost arm of the Baltic Sea. About 5% of the water mass in the Baltic Sea is located in the Gulf of Finland. The gulf is a continuation of the Baltic Proper without having any separating sill and can be characterised as a transition zone between brackish coastal sea and open sea conditions. The hydrological conditions are variable depending on the distance from the Baltic Proper. The small bays of the southern coast have good connection to the open Gulf of Finland and are strongly influenced by the main Baltic Sea current, upwelling and river inflow (Soomere et al., 2009). The eastern part is shallower and more brackish than western part of the gulf. Besides to the natural changes in the environmental conditions the Gulf of Finland suffers of major human pressures: high input of nutrients, organic matter and hazardous substances, as well as heavy maritime transport. The human impact is more evident in the coastal regions and in the smaller semi-enclosed bays where clearly pronounced changes in water quality and biodiversity can be observed. Therefore, the Gulf of Finland has been reported as one of the most polluted areas of the Baltic Sea (HELCOM, 2015). 2.2. Fish sampling and laboratory analyses The fish samples were collected in six sampling sites of the Gulf of Finland in 2013–14 (Fig. 1). The biological material used as a basis of present study was taken randomly. Baltic herring and sprat were sampled from Estonian commercial pelagic trawl fishery in western- and eastern part in the Gulf of Finland in October (herring) and April–May (sprat) 2013 and 2014. Perch, founder and salmon samples were taken from Estonian commercial coastal fishery in the western part of the Gulf of Finland in May 2013 and 2014. The biological material of

river lamprey was collected from commercial catch in the Kunda River in February 2014. The sampling sites for studied fish species are presented in Fig. 1. The total length and weight of sampled fish was measured. Additionally age, sex and maturity stage using six-grade scale (ICES, 2010) was assessed. Counting of the growth zones on otoliths was used to age herring and sprat. The opercular bones and scales were used for perch and salmon, respectively. Since the river lamprey lack any kind of age registering structures we used the mean age of spawners (Saat et al., 2003). Sampling process, biological analyses and compiling of biological material for chemical analyses followed requirements of Manual KJ I/ 16 (Biological tissue sampling from fish and molluscs for chemical analysis). The method (reg. No L179) is accredited by Estonian Accreditation Centre against the requirements of standards EVS-EN ISO/ITC 17025: 2006. 2.3. Chemical analyses 2.3.1. Polychlorinated biphenyls (PCB) and polybrominated diphenyl ethers (PBDE) After pooling and homogenization the samples were freeze-dried and fat was extracted with ethanol-toluene (15%/85% v/v) in Accelerated Solvent Extractor (Dionex ASE 300). After that solvent was exchanged to hexane and the fat content was determined gravimetrically. Further the samples were defatted on an acidic multilayer silica column and purified and fractionated on alumina and carbon columns. PCBs and PBDEs were analysed with GC/HRMS (Autospec Ultima) using selected ion monitoring mode with a 10,000 resolution. PCBs and PBDEs were separated on a DB5 MS column (60 m × 0.25 mm × 0.25 μm; for BDE209 the column length was 5 m). Status of the used instruments was assessed on a daily basis and the instruments were calibrated and serviced regularly. 13C-labelled PCB congeners (PCB 28, 52, 101, 138, 153, 180), were used as internal standards for PCBs. 13C-labelled PBDE standards (BDE 28, 47, 77, 99, 100, 153, 154, 183 ja 209) were used for quantification of PBDEs. The recoveries of the individual internal standards of PCB and PBDE congeners were determined by adding the recovery standards just before mass spectral

Fig. 1. Study area and sampling sites.



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laboratory T077). The scope of accreditation includes PCBs, PBDEs, and organic tin analyses from biological matrices. In addition to the internal quality control, the laboratory participates in several annual interlaboratory comparisons e.g. for food, feed, and environmental samples organized by Folkehelseinstituttet in Norway (PCBs and PBDEs), EU-Central Reference Laboratory in Germany (PCBs and PBDEs), Centre de Toxicologie in Canada and Intercind in Italy (PFAAs), and Quasimeme intercalibration trial (OTC).

analysis, and were 50–120%. The limits of quantification (LOQ) for individual congeners, which correspond to a signal-to-noise ratio of 3:1 (based on Commission Regulation (EU) No 252/2012) or concentration of the analyte in blank sample, were 0.1–9 pg/g for indicator-PCBs, and 0.1–31 pg/g for PBDEs, each expressed per wet weight of the sample. The expanded uncertainty of the method for sum of indicator PCBs was 20% and 15–40% for sum of PBDEs, depending on the concentration of the analytes in the sample. Two blank samples (a reagent blank and a methodological blank sample handled as the other samples) and one laboratory control sample of Baltic herring was run with every analysis batch with an allowable variation of ±20%.

3. Results All together 33 fish samples of six species – Baltic herring, sprat, flounder, perch, salmon, and river lamprey were collected and analysed. The mean biological parameters of samples on chemical substances are presented in the Table 1. All together 37 of PCB analogues, of which 12 were dioxin-like PCBs, were examined in fish except salmon and river lamprey. Six analogues (indicator PCBs) of ndl-PCB: CB 28, 52, 101, 138, 153, and 180, constitutes appr. 50% of PCB in fish studied. We also monitored content of 8 analogues of polybrominated diphenyl ethers (PBDE): BDE-28, 47, 99, 100, 153, 154, 183, and 209 in the fish. Over 50% of analysed PBDEs constitute analogue BDE-47. To characterise the content of perfluorinated compounds, the content of 13 analogues of PFAAs (PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFTrA, PFTeA, PFHxS, PFHpS, PFOS, and PFDS), was examined. The content of four analogues: PFHxA, PFHpA, PFTeA, and PFHpS was in all cases below the limit of quantitation. In order to characterise the content of organic tin compounds (OT) we used summarized content of four analogues: tributyltin TBT, dibutyltin DBT, diphenyltin TPhT, and dioctyltin DOT. The results of chemical analyse are presented in the Table 2.

2.3.2. Organic tin compounds (OT) The OT compounds analysed were mono-, di-, and tributyltin (MBT, DBT, TBT) and mono, di- and triphenyltin (MPhT, DPhT, TPhT) and dioctyltin (DOT). The analysis of freeze dried fish samples (0.25 g) was performed by solvent extraction, ethylation with sodium tetraethylborate and high resolution, GC/HRMS analysis according to the tissue method developed by Ikonomou et al. (Ikonomou et al., 2002) with slight modifications. Details of the method used have been described previously (Rantakokko et al., 2008; Rantakokko et al., 2010). Sum concentration of measured OTCs as ng organotin cation/g fresh weight (ng/g fw) is denoted as ΣOTCs. In the calculations of ΣOTCs, results less than the limit of quantification (bLOQ) were treated as zero. LOQs ranged from 0.1 to 1.1 ng/g fw depending on the compound. Two laboratory reagent blank samples were treated and analysed as the actual samples in each series of samples. Average mass of blank samples was subtracted from the results of actual fish samples. Certified mussel tissue CRM 477 was analysed in every series of samples. It has certified concentrations for MBT, DBT, and TBT, and indicative concentrations for MPhT, DPhT, and TPhT, respectively (Pellegrino et al., 2000).

4. Discussion 4.1. Polychlorinated biphenyls (PCB)

2.3.3. Perfluorinated compounds (PFAS) For quantitation prior to an extraction procedure a 2.5 ng of mass labelled internal standards in 50 μL 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. The samples were centrifuged at 2500 rpm for 10 min. The supernatants were collected. The extracts were evaporated to dryness under a flow of nitrogen and reconstituted to 300 μL of 60% aqueous methanol. Prior to instrumental analysis, the samples were filtered with 0.2 μm syringe filter (Pall Life Sciences, Ann Arbor, MI). The PFAS were analysed using liquid chromatography negative ion electrospray tandem mass spectrometry (LC–ESI–MS/ MS). Details of the LC–ESI–MS/MS parameters and quantitation have been presented earlier (Koponen et al., 2013). Measurement uncertainty of PFAS was 30%. The chemical analyses were carried out at the Chemicals and Health Unit of the National Institute for Health and Welfare (THL), which has been accredited according to the ISO 17025 standard by FINAS (testing

To characterise the content of polychlorinated biphenyls (PCB) in human food the summary content of six PCBs, namely indicator PCBs (ind-PCBs) – CB 28, 52, 101, 138, 153 and 180, equals approximately to half of the PCB content in fish samples is used. The maximum allowable EU concentration threshold of ind-PCBs in fish is 75 ng/g in w.w. (Commission Regulation (EC) No 1881/2006). Since PCBs are lipid-soluble compounds, their concentration is usually higher in fish of higher fat content (flounder, sprat, salmon) and lower in less fatty species like perch (Fig. 2) when the results are expressed as wet weight basis. The highest concentrations of ind-PCBs were observed in the flounder of the Western Gulf of Finland (Muuga Bay) and in herring of Eastern part of the Gulf. At the same time even the highest values of ind-PCB did not exceed one third of maximum allowed limit. The maximum content of ind-PCB (11.6 ng/g w.w.) in sprat of the Western Gulf of Finland remained 7- fold below the allowed EU limits.

Table 1 The mean biological parameters (±SE) and the content of dry matter and lipids in studied fish species. n

TL, cm

TW, g

Condition index, Cl

Age

Dry matter, %

Lipids, %

Eastern Gulf of Finland Baltic herring

6

16.6 ± 0.1

32.0 ± 0.6

0.70 ± 0.01

4.0 ± 0.1

23.5 ± 0.3

5.03 ± 0.31

Western Gulf of Finland Baltic herring Sprat Perch Flounder Salmon River lamprey

6 6 6 6 1 2

13.4 10.8 21.0 26.1 77.9 32.1

14.4 ± 0.3 8.2 ± 0.1 126 ± 10 204 ± 11 61.32 62.4 ± 4.3

0.64 0.79 0.63 0.64 1,25 –

2.5 2.3 4.5 4.8 5.0 6.5

22.8 30.1 21.6 25.5 34.4 37.5

4.59 13.1 1.18 4.87 12.3 18.6

± ± ± ±

0.1 0.1 0.5 0.4

± 0.5

± ± ± ±

0.01 0.02 0.01 0.02

± ± ± ±

0.1 0.1 0.2 0.3

± 0.0

± ± ± ±

0.4 0.5 0.2 0.8

± 0.6

± ± ± ±

0.22 0.40 0.04 0.65

± 1.3

TL = total length. TW = total weight.


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Table 2 The mean content (avg ± SE) of persistent organic pollutants (ng/g) in studied fish species (w.w.) in 2013–14. Σ PCB

Σ PBDE

Σ PFC

Σ OT

38.3 ± 2.2

0.63 ± 0.12

5.01 ± 0.28

10.9 ± 0.8

7.85 ± 0.84 3.43 ± 0.11 7.90 ± 1.53

Perch

3.2 ± 0.5

5.9 ± 1.0

0.37 ± 0.02 0.56 ± 0.02 0.35 ± 0.04 0.12 ± 0.02 1.20 2.02 ± 1.16

5.33 ± 0.49 8.90 ± 1.04

Flounder

10.6 ± 0.5 18.6 ± 4.9

18.5 ± 0.2 21.5 ± 0.8 35.6 ± 9.4

Species

ind PCB

Eastern Gulf of Finland Baltic herring 17.8 ± 1.2

Western Gulf of Finland Baltic herring 9.1 ± 0.1 Sprat

Salmon – River lamprey –

– –

7.69 ± 0.82 9.43 ± 2.71 5.47 5.85 ± 0.74

5.57 ± 1.22

Fig. 3. The content of eight summarized PBDE analogues in studied fishes of the Gulf of Finland.

14.9 14.2 ± 1.1

4.3. Perfluorinated compounds (PFAS) When compared to the results of studies carried out in 2003 and 2007–2008 (Margna and Reinik, 2009), our results show that the contents of six ind-PCB analogues were still below the limit values and even lower in flounder (resp. 30.6 and 18.6 ng/g in w.w.) and in sprat (resp. 12.9 and 10.6 ng/g w.w.). At the same time our results indicate that the mean ind-PCB content in herring was higher compared to the values obtained from various projects of Estonian Ministry of Rural Affairs and Veterinary and Food Board in 2006–2010. The respective values were 8.2 ± 0.4 and 9.1 ± 0.1 ng/g (w.w.) in the western and 10.8 ± 0.8 and 17.8 ± 1.2 ng/g (w.w.) in eastern part of the Gulf. However even these figures remain below the limit threshold, suggesting that the studied species do not cause any health risk at present.

4.2. Polybrominated diphenyl ethers (PBDE) According to the EFSA guidelines (2011) eight analogues of polybrominated diphenyl ethers (BDE-28, -47, -99, -100, -153, -154, -183, -209) should be monitored in the sea environment. Our results revealed that BDE-47 clearly dominated in the studied fishes. Since PBDEs are lipid-soluble compounds, the summary content was always higher in fat-rich species in wet weight bases: river lamprey, salmon and herring in the Eastern Gulf of Finland (Fig. 3). The mean summary content of eight analogues of PBDEs ranged from 0.37 ± 0.02 to 0.63 ± 0.12 ng/g (w.w.) in Western and Eastern Gulf of Finland, respectively. Such a wide variation: 0.46–0.71 ng/g (w.w.) was observed also in 2006–2011 (Roots et al., 2010). The content of PBDE was considerably higher in bigger/older herring (Tables 1 and 2). The average PBDE content in sprat also varied in wide range: 2006 and 2010 0.85 ± 0.02 and 0.18 ± 0.01 ng/g (w.w.) in 2006 and 2010 and on average 0.56 ± 0.02 ng/g (w.w.) in the western part of the Gulf in 2013–2014.

Fig. 2. The content of ind-PCBs in studied fish of the Gulf of Finland.

Altogether the content of 13 different PFNA compounds: PFHpA (perfluoroheptanoic acid), PFOA (perfluorooctanoic acid), PFNA (perfluorononanoic acid), PFDA (perfluorodecanoic acid), PFUnA (perfluoroundecanoic acid), PFDoA (perfluorododecanoic acid), PFTrA (perfluorotridecanoic acid), PFTeA (perfluorotetradecanoic acid), PFHxS (perfluorohexane sulfonate), PFHpS (perfluoroheptane sulfonate), PFOS (perfluorooctane sulfonate), and PFDS (perfluorodecane sulfonate), were studied in the fish of the Gulf of Finland in 2013– 2014. The concentrations of PFHxA, PFHpA, PFTeA and PFHpS remained in all cases below the limit of quantitation. The summary content of 13 PFAs analogues in perch, sprat and flounder was somewhat higher in the western part of the Gulf of Finland when compared to the eastern part of the Gulf of Finland (Fig. 4). The content of PFOA remained under the LOQ in all samples collected during present study in 2013–2014. In this respect our results were similar to those of reported for the Finnish coastal waters in 2009– 2010. The content of PFOS in herring, perch and salmon generally remained below 1–5 ng/g (w.w.) in both studies (Hallikainen et al., 2011). However the content of PFOS found in more polluted areas near the ports of the Helsinki City may be substantially higher, reaching for example 16–40 ng/g in w.w. (Hallikainen et al., 2011). The overall average content of PFOS in Baltic Sea fish muscle tissues: 1.5–5.3 μg/kg (w.w.) remains below the limit of quantitation (BSEP, 2010).

4.4. Organotin compounds (OT) To characterise the content of organotin compounds (OT) the summary content of four compounds TBT, DBT, TPhT, and DOT is used. The OT content was higher in salmon, river lamprey, and in herring in the Eastern Gulf of Finland. The lowest content was observed in sprat (Fig. 5).

Fig. 4. The summary content of 13 PFAS compounds in studied fish in the Gulf of Finland.



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Acknowledgement The work presented in this paper was funded by the Estonian Ministry of Rural Affairs, research project 3.4-29/334. We thank the laboratory technicians in the Chemicals and Health Unit at the National Institute for Health and Welfare for an excellent analytical work performed. References

Fig. 5. The content of organotin compounds in studied fishes of the Gulf of Finland.

The OT content in Estonian coastal fishes was also investigated within the HELCOM Project “Screening of hazardous substances in the eastern Baltic Sea”. According to the results the content of TBT in the herring of the Gulf of Finland varied from 3 to 8 ng/g (w.w) except one sample from the impact area of the Port of Sillamäe (34 ng/g w.w.). At the same time, the TBT content in perch and flounder remained below the limit of quantification and that of DPhT was 1–3.1 and 6.5 ng/g in w.w., respectively (Lilja et al., 2009). The Estonian Environmental Research Centre also studied the content of TBT in the perch liver tissue in 2010. The content varied from 2 to 46 μg/kg in d.w. in the Western Gulf of Finland. The high content of TBT observed in some samples can probably be explained with the location of sampling sites in the vicinity of ports of the Pakri Bay. The impact areas of ports often can be characterised by the elevated concentration of OT compounds in sediments and fishes (Lilja et al., 2009; Roots and Nõmmsalu, 2011.) In total, the OT level in fishes in Estonian coastal waters was low in 2013–2014 and below the EFSA limit threshold.

5. Conclusions The observed content of PCBs was always higher in wet weight bases in fatty fishes like flounder, herring and sprat. As a rule, the content of PCBs of Baltic herring was higher in the eastern part of the Gulf of Finland. However, even the highest content of ind-PCBs in fish did not exceed the maximum allowable EU concentration values. The highest concentrations of PBDEs were also recorded in fatty species – river lamprey and salmon. The mean content of PBDE was also considerably higher in older (5 years and older) herring from the eastern part of the Gulf of Finland. The concentrations of organic tin were highest in the species with high fat content –salmon, river lamprey and flounder. The higher values of pollutant were recorded also in herring from the eastern- and in older (5 years and older) herring from the western part of the Gulf of Finland. As a rule of thumb the content of PFAS in the fish of the Gulf of Finland was low. The concentration of four PFAS analogues – PFHxA, PFHpA, PFTeA and PFHpS, were below the limit of quantitation. Only in perch, sprat and flounder living in the vicinity of the Port of Muuga (western part of the Gulf of Finland) the content of summarized PFAS was a bit higher. While the content of several persistent organic compounds (PBDE, organotin etc.) were considerably higher in fatty and older fishes is very important to link pollutant content to lipid content of fish following its seasonal variation.

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