Skip to main content
Log in

Survey of patterns, levels, and trends of perfluorinated compounds in aquatic organisms and bird eggs from representative German ecosystems

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Purpose

Samples from the German Environmental Specimen Bank (ESB) covering particularly the years 1994–1996, 2000–2002, and 2006–2009 were analyzed for perfluorinated compounds (PFC; mainly C4–C13 carboxylic and sulfonic acids) to gain an overview on current PFC levels and patterns in marine, limnetic, and terrestrial biota; to assess their concentrations in different trophic levels; and to investigate whether risk management measures for PFC are successful.

Methods

Specimens, either standardized annual pooled samples (blue mussels, eelpout liver, bream liver, pigeon eggs) or individual single samples (cormorant eggs, rook eggs), were collected for the German ESB program from representative sampling sites according to documented guidelines. After appropriate extraction, PFC were quantified under ISO/IEC 17025 accreditation by HPLC/MS-MS with isotopically labeled internal standards. Limits of quantification (LOQs) were 0.2–0.5 ng/g. Data are reported on a wet weight basis.

Results and discussion

In most samples the predominant PFC was perfluorooctane sulfonic acid (PFOS). However, in marine mussels from North and Baltic Seas, PFOS levels were mostly below the LOQ, but low residues of PFOS amide were found which declined in recent years. Livers of eelpout showed maximum concentrations of 15–25 ng/g PFOS in the period 2000–2002 and low amounts of perfluoropentanoate in all years. Beside PFOS (median 48 ng/g) several PFC could be determined in cormorant eggs sampled in 2009 from a Baltic Sea site. For a freshwater ecosystem, current PFC burdens for cormorant eggs were even higher (median 400 ng/g PFOS). Livers of bream from rivers showed concentrations of 130–260 ng/g PFOS, but for bream from a reference lake levels were only about 6 ng/g. In contrast to cormorants, eggs of rook and feral pigeon from terrestrial ecosystems displayed only low PFC burdens (up to 6 ng/g PFOS).

Conclusions

Generally, PFC levels were lower in marine than in freshwater biota. PFC burdens were higher in biota from the ESB-North Sea sites than in Baltic Sea organisms. Levels of PFC were quite high especially in top predators of both limnetic and marine ecosystems. Only low PFC levels were detected in eggs of terrestrial birds. A decrease of PFOS levels from maximum values around the year 2000 observed at least in North Sea biota may be a result of a production cease and shifts in marketing pattern.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • 3M (2010). http://solutions.3m.com/wps/portal/3M/en_US/PFOS/PFOA/Information/phase-out-technologies/. Accessed 22 Feb 2011

  • Ahrens L, Siebert U, Ebinghaus R (2009) Temporal trends of polyfluoroalkyl compounds in harbor seals (Phoca vitulina) from the German Bight, 1999–2008. Chemosphere 76:151–158

    Article  CAS  Google Scholar 

  • Ahrens L, Herzke D, Huber S, Bustnes JO, Bangjord G, Ebinghaus R (2011) Temporal trends and pattern of polyfluoroalkyl compounds in tawny owl (Strix aluco) eggs from Norway, 1986–2009. Environ Sci Technol. doi:10.1021/es103473v

  • Andersen ME, Butenhoff JL, Chang S-C, Farrar DG, Kennedy GL Jr, Lau C, Olsen GW, Seed J, Wallace KB (2008) Review: perfluoroalkyl acids and related chemistries—toxicokinetics and modes of action. Toxicol Sci 102:3–14

    Article  CAS  Google Scholar 

  • Becker AM, Gerstmann S, Frank H (2010) Perfluorooctanoic acid and perfluorooctane sulfonate in two fish species collected from the Roter Main River, Bayreuth, Germany. Bull Environ Contam Toxicol 84:132–135

    Article  CAS  Google Scholar 

  • Bignert A (2007) PIA statistical application developed for use by the Arctic Monitoring and Assessment Programme (www.amap.no). Accessed 22 Feb 2001

  • Bignert A, Danielsson S, Nyberg E, Asplund L, Eriksson U, Berger U, Haglund P (2009) Comments concerning the national Swedish contaminant monitoring programme in marine biota 2009. Swedish Museum of Natural History, Department of Contaminant Research, Stockholm, Sweden, 14.08.2009 http://www.nrm.se/download/18.6321786f122df65955f80002587/Marina+programmet+2009.pdf. Accessed 22 Feb 2011

  • BMU (2008) Federal Ministry for the Environment, nature conservation and nuclear safety: German Environmental Specimen Bank—concept. Federal Environment Agency (Umweltbundesamt), Berlin, Germany, 2008 http://www.umweltprobenbank.de/upb_static/fck/download/concept_oct_2008_en.pdf. Accessed on 22 Feb 2011

  • Bossi R, Riget FF, Dietz R, Sonne C, Fauser P, Dam M, Vorkamp K (2005) Preliminary screening of perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish, birds and marine mammals from Greenland and the Faroe Islands. Environ Pollut 136:323–329

    Article  CAS  Google Scholar 

  • Bossi R, Strand J, Sortkjaer O, Larsen MM (2008) Perfluoroalkyl compounds in Danish wastewater treatment plants and aquatic environments. Environ Int 34:443–450

    Article  CAS  Google Scholar 

  • Butt CM, Berger U, Bossi R, Tomy GT (2010) Levels and trends of poly- and perfluorinated compounds in the arctic environment. Sci Total Environ 408:2936–2965

    Article  CAS  Google Scholar 

  • Conder JM, Hoke RA, de Wolf W, Russell MH, Buck RC (2008) Are PFCAs bioaccumulative? A critical review and comparison with regulatory criteria and persistent lipophilic compounds. Environ Sci Technol 42:995–1003

    Article  CAS  Google Scholar 

  • Cunha I, Hoff P, van de Vijver K, Guilhermino L, Esmans E, de Coen W (2005) Baseline study of perfluorooctane sulfonate occurrence in mussels, Mytilus galloprovincialis, from north-central Portuguese estuaries. Mar Pollut Bull 50:1128–1132

    Article  CAS  Google Scholar 

  • DIN 32645 (1998) Chemical analysis—decision limit, detection limit and determination limit under repeatability conditions—terms, methods, evaluation. German Standard, Beuth Verlag, Berlin (in German language)

  • European Union (2006) Directive 2006/122/EC of the European Parliament and of the Council of 12 December 2006 amending for the 30th time Council Directive 76/769/EEC on the approximation of the laws, regulations and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations (perfluorooctane sulfonates). Official Journal of the European Union, L 372/32 EN December 27, 2006

  • German Federal Environment Agency (2009) Do without per- and polyfluorinated chemicals and prevent their discharge into the environment. Federal Environment Agency, Dessau-Rosslau, Germany http://www.umweltdaten.de/publikationen/fpdf-l/3818.pdf. Accessed 22 Feb 2011

  • Giesy JP, Kannan K (2001) Global distribution of perfluorooctane sulfonate in wildlife. Environ Sci Technol 35:1339–1342

    Article  CAS  Google Scholar 

  • Herzke D, Nygård T, Berger U, Huber S, Røv N (2009) Perfluorinated and other persistent halogenated organic compounds in European shag (Phalacrocorax aristotelis) and common eider (Somateria mollissima) from Norway: a suburban to remote pollutant gradient. Sci Total Environ 408:340–348

    Article  CAS  Google Scholar 

  • Hoff PT, Van de Vijver K, Van Dongen W, Esmans EL, Blust R, De Coen WM (2003) Perfluorooctane sulfonic acid in bib (Trisopterus luscus) and plaice (Pleuronectes platessa) from the Western Scheldt and the Belgian North Sea: distribution and biochemical effects. Environ Toxicol Chem 22:608–614

    CAS  Google Scholar 

  • Hoff PT, Van Campenhout K, Van de Vijver K, Covaci A, Bervoets L, Moens L, Huyskens G, Goemans G, Belpaire C, Blust R, De Coen W (2005) Perfluorooctane sulfonic acid and organohalogen pollutants in liver of three freshwater fish species in Flanders (Belgium): relationships with biochemical and organismal effects. Environ Pollut 137:324–333

    Article  CAS  Google Scholar 

  • Holmström KE, Järnberg U, Bignert A (2005) Temporal trends of PFOS and PFOA in guillemot eggs from the Baltic Sea, 1968–2003. Environ Sci Technol 39:80–84

    Article  Google Scholar 

  • Holmström KE, Johansson A-K, Bignert A, Lindberg P, Berger U (2010) Temporal trends of perfluorinated surfactants in Swedish peregrine falcon eggs (Falco peregrinus), 1974–2007. Environ Sci Technol 44:4083–4088

    Article  Google Scholar 

  • Houde M, Martin JW, Letcher RJ, Solomon KR, Muir DC (2006) Biological monitoring of polyfluoroalkyl substances: a review. Environ Sci Technol 40:3463–3473

    Article  CAS  Google Scholar 

  • Jones PD, Hu W, de Coen W, Newstedt JL, Giesy JP (2003) Binding of perfluorinated fatty acids to serum proteins. Environ Toxicol Chem 22:2639–2649

    Article  CAS  Google Scholar 

  • Kannan K, Franson JC, Bowerman WW, Hansen KJ, Jones PD, Giesy JP (2001) Perfluorooctane sulfonate in fish-eating water birds including bald eagles and albatrosses. Environ Sci Technol 35:3065–3070

    Article  CAS  Google Scholar 

  • Kannan K, Corsolini S, Falandysz J, Oehme G, Focardi S, Giesy JP (2002) Perfluorooctanesulfonate and related fluorinated hydrocarbons in marine mammals, fishes, and birds from coasts of the Baltic and the Mediterranean seas. Environ Sci Technol 36:3210–3216

    Article  CAS  Google Scholar 

  • Kannan K, Tao L, Sinclair E, Pastva SD, Jude DJ, Giesy JP (2005) Perfluorinated compounds in aquatic organisms at various trophic levels in a Great Lakes food chain. Arch Environ Contam Toxicol 48:559–566

    Article  CAS  Google Scholar 

  • Klein R, Bartel M, Neitzke M, Nentwich K, Paulus M, Quack M, Wagner G (2003) Umweltprobenbank: guideline for sampling and sample treatment—bream (Abramis brama). University of Trier, Institute for Biogeography, Trier

    Google Scholar 

  • Klein R, Bartel M, Paulus M, Quack M, Tarricone K, Teubner D, Wagner G (2007) Umweltprobenbank: guideline for sampling and sample treatment—eelpout (Zoarces viviparus). University of Trier, Institute for Biogeography, Trier

    Google Scholar 

  • Müller J, Jürling H (2008) Retrospective monitoring of perfluorinated compounds in eggs of sea gulls and pigeons, and in deer liver samples. Report of Fraunhofer IME for German Federal Environment Agency, Dessau-Rosslau (in German language with English abstract)

  • Nicholson M D, Fryer R, Larsen J R (1998) Temporal trend monitoring: robust method for analysing contaminant trend monitoring data. Techniques in marine environmental sciences, No. 20. ICES, Copenhagen

  • Paul AG, Jones KC, Sweetman AJ (2009) A first global production, emission, and environmental inventory for perfluorooctane sulfonate. Environ Sci Technol 43:386–392

    Article  CAS  Google Scholar 

  • Paulus M, Klein R, Wagner G, Müller P (1996) Biomonitoring and environmental specimen banking. Environ Sci Pollut Res 3:169–177

    Article  CAS  Google Scholar 

  • Paulus M, Bartel M, Klein R, Neitzke M, Nentwich K, Quack M, Wagner G (2003a) Umweltprobenbank: guideline for sampling and sample treatment—feral pigeon (Columba livia f. domestica). University of Trier, Institute for Biogeography, Trier

    Google Scholar 

  • Paulus M, Bartel M, Klein R, Neitzke M, Nentwich K, Quack M, Wagner G (2003b) Umweltprobenbank: guideline for sampling and sample treatment: herring gull (Larus argentatus). University of Trier, Institute for Biogeography, Trier

    Google Scholar 

  • Rüdel H, Lepper P, Steinhanses J, Schröter-Kermani C (2003) Retrospective monitoring of organotin compounds in marine biota from 1985 to 1999: results from the German environmental specimen bank. Environ Sci Technol 37:1731–1738

    Article  Google Scholar 

  • Rüdel H, Böhmer W, Schröter-Kermani C (2006) Retrospective monitoring of synthetic musk compounds in aquatic biota from German rivers and coastal areas. J Environ Monit 8:812–823

    Article  Google Scholar 

  • Rüdel H, Müller J, Jürling H, Schröter-Kermani C (2010) Retrospective monitoring of perfluorinated compounds in archived herring gull eggs. In: Isobe T, Nomiyama K, Subramanian A, Tanabe S (eds) Interdisciplinary studies on environmental chemistry—environmental specimen bank: exploring possibility of setting-up ESBs in developing countries. TERRAPUB, Tokyo, pp 81–86. ISBN 978-4-88704-153-0

    Google Scholar 

  • Salmi T, Määttä A, Anttila P, Ruoho-Airola T, Amnell T (2002) Detecting trends of annual values of atmospheric pollutants by the Mann–Kendall test and Sen’s slope estimates—the EXCEL template application MAKESENS. Report code FMI-AQ-31. Finnish Meteorological Institute, Helsinki

    Google Scholar 

  • So MK, Taniyasu S, Lam PK, Zheng GJ, Giesy JP, Yamashita N (2006) Alkaline digestion and solid phase extraction method for perfluorinated compounds in mussels and oysters from South China and Japan. Arch Environ Contam Toxicol 50:240–248

    Article  CAS  Google Scholar 

  • Tomy GT, Pleskach K, Ferguson SH, Hare J, Stern G, MacInnis G, Marvin CH, Loseto L (2009) Trophodynamics of some PFC and BFRs in a western Canadian arctic marine food web. Environ Sci Technol 43:4076–4081

    Article  CAS  Google Scholar 

  • Umweltbundesamt (1996) Umweltprobenbank des Bundes—Verfahrensrichtlinien. Erich Schmidt Verlag, Berlin

    Google Scholar 

  • UNEP (2009) Report of the Conference of the parties of the Stockholm Convention on Persistent Organic Pollutants on the work of its fourth meeting, Geneva, 4–8 May 2009. Document UNEP/POPS/COP.4/38. http://chm.pops.int/Portals/0/Repository/COP4/UNEP-POPS-COP.4-38.English.pdf. Accessed 22 Feb 2011

  • Van den Heuvel JP, Kuslikis BI, Peterson RE (1992) Covalent binding of perfluorinated fatty acids to proteins in the plasma, liver and testes of rats. Chem Biol Interact 82:317–328

    Article  Google Scholar 

  • Verreault J, Berger U, Gabrielsen GW (2007) Trends of perfluorinated alkyl substances in herring gull eggs from two coastal colonies in northern Norway 1983–2003. Environ Sci Technol 41:6671–6677

    Article  CAS  Google Scholar 

  • Wagner G, Bartel M, Klein R, Paulus M, Quack M, Tarricone K, Teubner D (2007) Umweltprobenbank: guideline for sampling and sample treatment—blue mussel (Mytilus edulis). University of Trier, Institute for Biogeography, Trier

    Google Scholar 

  • Wenzel A, Böhmer W, Müller J, Rüdel H, Schröter-Kermani C (2004) Retrospective monitoring of alkylphenols and alkylphenol monoethoxylates in aquatic biota from 1985 to 2001: results from the German environmental specimen bank. Environ Sci Technol 38:1654–1661

    Article  CAS  Google Scholar 

  • Yoshikane M, Takazawa Y, Tanaka A, Komori S, Kobayashi M, Kanda Y, Jahan N, Shibata Y (2006) Concentration of perfluorochemicals in bivalves in Japan by alkaline digestion method. Organohalog Compd 68:2063–2066

    CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge the contributions of all past and present partners of the Umweltprobenbank program to the routine operations of the specimen bank since these are the basis of all retrospective investigations. The continuous funding of the program by the German Federal Ministry of the Environment, Nature Conservation and Nuclear Safety is gratefully acknowledged.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Heinz Rüdel.

Additional information

Responsible editor: Ake Bergman

This paper is a contribution to the series: “Chemical and Biological Environmental Monitoring (CBEM)” of the German Working Group on Environmental Monitoring (editors: H. Rüdel, Schmallenberg; W. Schröder, Vechta; K. T. von der Trenck, Karlsruhe; G. A. Wiesmüller, Cologne)

Electronic supplementary materials

Below is the link to the electronic supplementary material.

ESM

(DOC 448 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rüdel, H., Müller, J., Jürling, H. et al. Survey of patterns, levels, and trends of perfluorinated compounds in aquatic organisms and bird eggs from representative German ecosystems. Environ Sci Pollut Res 18, 1457–1470 (2011). https://doi.org/10.1007/s11356-011-0501-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-011-0501-9

Keywords

Navigation