Skip to main content
SpringerLink
Log in

Monitoring of hexabromocyclododecane diastereomers in fish from European freshwaters and estuaries

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

Abstract

Background and aims

Hexabromocyclododecane (HBCD) is a brominated flame retardant used mainly in polystyrene foam as well as in textile applications. In recent years, measures were taken to reduce HBCD emissions during its production and use. To evaluate the efficacy of these measures, a monitoring project was initiated with fish as bioaccumulation indicators.

Methods

Since 2007 bream was sampled annually at several European freshwater sites applying standardized methods. Muscle samples were analyzed by a validated liquid chromatography–tandem mass spectrometry (LC-MS/MS) method which allows the quantification of α-, β-, and γ-diastereomers of HBCD.

Discussion

In most samples, α-HBCD was predominant. The lowest HBCD levels (11 μg/kg lipid weight (lw), sum of three HBCD diastereomers) were detected in bream sampled in 2009 from Lake Belau which is situated in a rural area of Northern Germany. During the 4-year study period, statistical significant decreases of HBCD concentrations were detected in bream from the rivers Rhone (France; −85%, level 2010, 205 μg/kg lw) and Western Scheldt (the Netherlands; −60%, level 2010, 36 μg/kg lw). High HBCD concentrations (9,480–14,500 μg/kg lw) without a clear time trend were observed in bream from the river Tees (UK). These high levels are in line with published data for fish from contaminated regions.

Conclusions

Overall, the results indicate that environmental burdens of HBCD are decreasing at those locations where point sources and more diffuse emissions are expected.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

Similar content being viewed by others

References

  • Bignert A (2007) PIA statistical application developed for use by the Arctic Monitoring and Assessment Programme (Trend Analysis Package). http://www.amap.no/documents/index.cfm?dirsub=/PIA%20Trend%20Analysis%20Package. Accessed 08 August 2011

  • Boehmer W, Ruedel H, Wenzel A, Schroeter-Kermani C (2004) Retrospective monitoring of triclosan and methyl-triclosan in fish: results from the German environmental specimen bank. Organohalogen Comp 66:1489–1494. http://www.dioxin20xx.org/pdfs/2004/04-645.pdf. Accessed 08 August 2011

    Google Scholar 

  • Bogdal C, Naef M, Schmid P, Kohler M, Zennegg M, Bernet D, Scheringer M, Hungerbühler K (2009) Unexplained gonad alterations in whitefish (Coregonus spp.) from Lake Thun, Switzerland: levels of persistent organic pollutants in different morphs. Chemosphere 74:434–440

    Article  CAS  Google Scholar 

  • Bromley PJ (2003) The use of market sampling to generate maturity ogives and to investigate growth, sexual dimorphism and reproductive strategy in central and south-western North Sea sole (Solea solea L.). ICES J Marine Sci 60:52–65. http://icesjms.oxfordjournals.org/cgi/reprint/60/1/52.pdf. Accessed 08 August 2011

  • Cheaib Z, Grandjean D, Kupper T, de Alencastro LF (2009) Brominated flame retardants in fish of Lake Geneva (Switzerland). Bull Environ Contam Toxicol 82:522–527

    Article  CAS  Google Scholar 

  • COT (2004) Committee on toxicity of chemicals in food consumer products and the environment: statement on brominated flame retardants in fish from the Skerne–Tees Rivers system. Corrected version April 2004. http://cot.food.gov.uk/pdfs/bfrstatement.pdf. Accessed 08 August 2011

  • Covaci A, Gerecke AC, Law RJ, Voorspoels S, Kohler M, Heeb NV, Leslie H, Allchin CR, de Boer J (2006) Hexabromocyclododecanes (HBCDs) in the environment and humans: a review. Environ Sci Technol 40:3679–3688

    Article  CAS  Google Scholar 

  • EBFRIP (2010) European brominated flame retardant industry panel. The voluntary emissions control action programme—measurable achievements. Annual Progress Report 2009. Brussels, Belgium. http://www.vecap.info/uploads/VECAP_report_22%2001.pdf. Accessed 08 August 2011

  • ECHA (2008) Data on manufacture, import, export, uses and releases of HBCDD as well as information on potential alternatives to its use. European Chemicals Agency, Helsinki, Finland, 108 pp. http://echa.europa.eu/doc/consultations/recommendations/tech_reports/tech_rep_hbcdd.pdf. Accessed 08 August 2011

  • Eljarrat E, de la Cal A, Raldua D, Duran C, Barcelo D (2004) Occurrence and bioavailability of polybrominated diphenyl ethers and hexabromocyclododecane in sediment and fish from the Cinca River, a tributary of the Ebro River (Spain). Environ Sci Technol 38:2603–2608

    Article  CAS  Google Scholar 

  • Esslinger S, Becker R, Jung C, Schröter-Kermani C, Bremser W, Nehls I (2011) Temporal trend (1988–2008) of hexabromocyclododecane enantiomers in herring gull eggs from the German coastal region. Chemosphere 83:161–167

    Article  CAS  Google Scholar 

  • European Commission (2000) SANCO/3029/99 rev.4 (11/07/2000): Residues: guidance for generating and reporting methods of analysis in support of pre-registration data requirements for Annex II (part A, Section 4) and Annex III (part A, Section 5) of Directive 91/414. Directorate General Health and Consumer Protection, Brussels. http://ec.europa.eu/food/plant/protection/evaluation/guidance/wrkdoc12_en.pdf. Accessed 08 August 2011

  • European Commission (2004) SANCO/825/00 rev. 7 (17/03/2004): Guidance document on residue analytical methods. Directorate General Health and Consumer Protection, Brussels. http://ec.europa.eu/food/plant/protection/resources/guide_doc_825-00_rev7_en.pdf. Accessed 08 August 2011

  • European Commission (2008) Risk assessment hexabromocyclododecane, CAS-No. 25637-99-4, EINECS No. 247-148-4. Final Report. May 2008, 507 pp. http://esis.jrc.ec.europa.eu/doc/existing-chemicals/risk_assessment/REPORT/hbcddreport044.pdf. Accessed 08 August 2011

  • Gerecke AC, Kohler M, Zennegg M, Schmid P, Heeb NV (2003) Detection of α-isomer dominated HBCD (hexabromocyclododecane) in Swiss fish at levels comparable to PBDEs (polybrominated diphenyl ethers). Organohalogen Compd 61:155–158. http://www.dioxin20xx.org/pdfs/2003/03-177.pdf. Accessed 08 August 2011

  • Hajslová J, Pulkrabová J, Poustka J, Cajka T, Randák T (2007) Brominated flame retardants and related chlorinated persistent organic pollutants in fish from river Elbe and its main tributary Vltava. Chemosphere 69:1195–1203

    Article  Google Scholar 

  • Harrad S, Abdallah MA, Rose NL, Turner SD, Davidson TA (2009) Current-use brominated flame retardants in water, sediment, and fish from English lakes. Environ Sci Technol 43:9077–9083

    Article  CAS  Google Scholar 

  • Heeb NV, Schweizer WB, Kohler M, Gerecke AC (2005) Structure elucidation of hexabromocyclododecanes—a class of compounds with a complex stereochemistry. Chemosphere 61:65–73

    Article  CAS  Google Scholar 

  • Hrádková P, Pulkrabová J, Kalachová K, Hloušková V, Tomaniová M, Poustka J, Hajšlová J (2011) Occurrence of halogenated contaminants in fish from selected river localities and ponds in the Czech Republic. Arch Environ Contam Toxicol. doi:10.1007/s00244-011-9681-z

  • ISO/IEC 17025 (2005) General requirements for the competence of testing and calibration laboratories. International Organization for Standardization, Geneva, Switzerland

  • Janák K, Covaci A, Voorspoels S, Becher G (2005) Hexabromocyclododecane in marine species from the Western Scheldt estuary: diastereoisomer- and enantiomer-specific accumulation. Environ Sci Technol 39:1987–1994

    Article  Google Scholar 

  • Klein R (1993) The animal specimens of terrestrial and limnetic ecosystems in the environmental specimen banking programme of Germany. Sci Total Environ 139–140:203–212

    Google Scholar 

  • Klein R, Bartel M, Paulus M, Quack M, Tarricone K, Teubner D, Wagner G (2010a) Umweltprobenbank des Bundes: guideline for sampling and sample treatment—bream (Abramis brama). Biogeography, Trier University, Trier, Germany, Version V 2.0.1. http://www.umweltprobenbank.de/upb_static/fck/download/SOP_Bream.pdf. Accessed 08 August 2011

  • Klein R, Bartel M, Paulus M, Quack M, Tarricone K, Teubner D, Wagner G (2010b) Umweltprobenbank des Bundes: guideline for sampling and sample treatment—eelpout (Zoarces viviparus). Biogeography, Trier University, Trier, Germany. Version V 2.0.1. http://www.umweltprobenbank.de/upb_static/fck/download/SOP_Eelpout.pdf. Accessed 08 August 2011

  • Law RJ, Bersuder P, Allchin CR, Barry J (2006) Levels of the flame retardants hexabromocyclododecane and tetrabromobisphenol A in the blubber of harbour porpoises (Phocoena phocoena) stranded or bycaught in the U.K, with evidence for an increase in HBCD concentrations in recent years. Environ Sci Technol 40:2177–2183

    Article  CAS  Google Scholar 

  • Law RJ, Bersuder P, Barry J, Wilford BH, Allchin CR, Jepson PD (2008a) A significant downturn in levels of hexabromocyclododecane in the blubber of harbor porpoises (Phocoena phocoena) stranded or bycaught in the UK: an update to 2006. Environ Sci Technol 42:9104–9109

    Article  CAS  Google Scholar 

  • Law RJ, Herzke D, Harrad S, Morris S, Bersuder P, Allchin CR (2008b) Levels and trends of HBCD and BDEs in the European and Asian environments, with some information for other BFRs. Chemosphere 73:223–241

    Article  CAS  Google Scholar 

  • Li ZH, Zlabek V, Turek J, Velisek J, Pulkrabova J, Kolarova J, Sudova E, Berankova P, Hradkova P, Hajslova J, Randak T (2011) Evaluating environmental impact of STPs situated on streams in the Czech Republic: an integrated approach to biomonitoring the aquatic environment. Water Res 45:1403–1413

    Article  CAS  Google Scholar 

  • Nicholson MD, Fryer R, Larsen JR (1998) Temporal trend monitoring: robust method for analysing contaminant trend monitoring data. Techniques in Marine Environmental Sciences, No. 20. ICES, Copenhagen

  • 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 

  • Pulkrabová J, Hajslová J, Poustka J, Kazda R (2007) Fish as biomonitor of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in aquatic environment: pollution of Elbe River-basin. Environ Health Perspect 115(suppl 1):28–34

    Article  Google Scholar 

  • Roosens L, Dirtu AC, Goemans G, Belpaire C, Gheorghe A, Neels H, Blust R, Covaci A (2008) Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium. Environ Int 34:976–983

    Article  CAS  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, Uhlig S, Weingärtner M (2008) Umweltprobenbank des Bundes: guidelines for sampling and sample processing: pulverisation and homogenisation of environmental samples by cryomilling. Fraunhofer IME, Schmallenberg, Germany. Version V 2.0.0. http://www.umweltprobenbank.de/upb_static/fck/download/IME_SOP_preparation_Dez2008_V200.pdf. Accessed 08 August 2011

  • 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, Finland

  • Smedes F (1999) Determination of total lipid using non-chlorinated solvents. Analyst 124:1711–1718

    Article  CAS  Google Scholar 

  • Stiehl T, Körner A, Ricking M, Sawal G, Warmbrunn-Suckrow E, Lepom P (2008) PBDE and HBCD levels in surface sediments from German rivers. Organohalogen Compd. 70:1590–1593. http://www.dioxin20xx.org/pdfs/2008/08-718.pdf. Accessed 08 August 2011

    Google Scholar 

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

  • Umweltbundesamt (2008) German environmental specimen bank—concept. Umweltbundesamt, Berlin, Germany. http://www.umweltprobenbank.de/upb_static/fck/download/concept_oct_2008_en.pdf. Accessed 08 August 2011

  • UNEP (2004) Guidance for a global monitoring programme for persistent organic pollutants, 1st edn, June 2004. Prepared by UNEP Chemicals, Geneva, Switzerland. http://www.chem.unep.ch/gmn/guidancegpm.pdf. Accessed 08 August 2011

  • UNEP (2010) Risk profile: hexabromocyclododecane. Stockholm Convention on Persistent Organic Pollutants. Document UNEP/POPS/POPRC.6/10. Review Committee, 11–15 October 2010. http://chm.pops.int/Convention/POPsReviewCommittee/POPRCMeetings/POPRC6/POPRC6Documents/tabid/783/language/en-US/Default.aspx. Accessed 08 August 2011

  • Van der Oost R, Beyer J, Vermeulen NPE (2003) Fish bioaccumulation and biomarkers in environmental risk assessment: a review. Environ Toxicol Pharmacol 13:57–149

    Article  Google Scholar 

  • Veith GD, Defoe DL, Bergstedt BV (1979) Measuring and estimating the bioconcentration factor of chemicals in fish. J Fish Res Board Can 36:1040–1048

    Article  CAS  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 

Download references

Acknowledgments

The authors thank the European Flame Retardant Association (EFRA), the PlasticsEurope Association, and the European Extruded Polystyrene Insulation Boards Association (EXIBA) for the long-term funding of the project “Environmental Monitoring of HBCD.” The contributions of Walter Böhmer, Dr. Annette Fliedner, Diana Homrighausen, Jens Nowak, Sonja Uhlig, and Martin Weingärtner (Fraunhofer IME Schmallenberg), and Martina Bartel-Steinbach, Lena Wilms, and Christian Ehrmantraut (University of Trier) to the project are gratefully acknowledged.

Author information

Authors and Affiliations

  1. Fraunhofer Institute for Molecular Biology and Applied Ecology (Fraunhofer IME), 57392, Schmallenberg, Germany

    Heinz Rüdel & Josef Müller

  2. Department of Biogeography, University of Trier, 54286, Trier, Germany

    Markus Quack & Roland Klein

Authors
  1. Heinz Rüdel
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Josef Müller
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Markus Quack
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Roland Klein
    View author publications

    You can also search for this author in PubMed Google Scholar

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 material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 424 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rüdel, H., Müller, J., Quack, M. et al. Monitoring of hexabromocyclododecane diastereomers in fish from European freshwaters and estuaries. Environ Sci Pollut Res 19, 772–783 (2012). https://doi.org/10.1007/s11356-011-0604-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-011-0604-3

Keywords

Search

Navigation