The extensive application of halogenated flame retardants has led to their widespread distribution in the environment. Recently, concerns emerged regarding their potential persistence, (bio)accumulation, and/or toxicity. Particularly halogenated flame retardants based on norbornene structures, like Dechlorane Plus as well as other brominated PBDE replacements, generically called emerging, novel, or alternative flame retardants, are in the focus of interest. A comprehensive analytical method for the determination of 21 halogenated flame retardants (HFRs) of different substance classes (dechloranes, brominated aromates, brominated ethers, cyclic BFR) in a broad variety of matrices (tree leaves, fish fillet, birds eggs, suspended particles) was developed in order to assess their environmental levels as well as temporal trends, especially for the use within environmental specimen banks (ESBs). In addition to the alternative HFRs, a set of 24 PBDEs were measured in the same samples, however using GC-EI-MS for detection. Samples were extracted using accelerated solvent extraction (ASE) with dichloromethane:hexane (exception: soxhlet extraction for suspended particles) followed by a multi column clean-up. Quantification was performed by API-GC-MS/MS as a modern, gentle, and sensitive technique for simultaneous detection of compounds throughout a wide range of masses and fragmentation characteristics (exception: PBDE detection using GC-EI-MS). With the exception of BDE 209, instrumental precisions of target compounds ranged from 1% to 16 % (at levels of 2 pg injection–1 for HFR, 20 pg injection–1 for DBDPE, 7-36 pg injection–1 for PBDEs). Interday precisions of the entire analytical method including extraction and clean-up were mostly below 25% for all validation matrices at spiked levels of 100 pg sample–1 for HFR (DBDPE: 1000 pg sample–1) and 1200–6000 pg sample–1 for PBDEs. The majority of analytes were investigated with expanded measurement uncertainties of less than 50%.
Dechlorane Plus Brominated flame retardants nBFR German environment specimen bank Atmospheric pressure ionization
This is a preview of subscription content, log in to check access.
The authors thank their laboratory staff for the dedicated work on the project, particularly Kay Kelterer, Judith Söhler, and Steffi Rolle. The authors are grateful to Heinz Rüdel (Fraunhofer IME) as well as Caren Rauert and Peter Lepom (German Environment Agency) for valuable discussions. The German Environment Agency is acknowledged for funding (AZ 93 04/25).
Compliance with ethical standards
Herring gull egg sampling was performed as part of the routine operation of the German Federal Environmental Specimen Bank. It was approved by the state authorities and followed the respective guidelines.
Conflict of interest
The authors declare that they have no conflict of interest.
Kolic TM, Shen L, MacPherson K, Fayez L, Gobran T, Helm PA, et al. The analysis of halogenated flame retardants by GC-HRMS in environmental samples. J Chromatogr Sci. 2009;47:83–91.CrossRefGoogle Scholar
Chen D, Letcher RJ, Burgess NM, Champoux L, Elliott JE, Hebert CE, et al. Flame retardants in eggs of four gull species (Laridae) from breeding sites spanning Atlantic to Pacific Canada. Environ Pollut. 2012;168:1–9.CrossRefGoogle Scholar
Law RJ, Losada S, Barber JL, Bersuder P, Deaville R, Brownlow A, et al. Alternative flame retardants, Dechlorane Plus and BDEs in the blubber of harbour porpoises (Phocoena phocoena) stranded or caught in the UK during 2008. Environ Int. 2013;60:81–8.CrossRefGoogle Scholar
Guerra P, Fernie K, Jimenez B, Pacepavicius G, Shen L, Reiner E, et al. Dechlorane Plus and related compounds in Peregrine falcon (Falco peregrinus) eggs from Canada and Spain. Environ Sci Technol. 2011;45:1284–90.CrossRefGoogle Scholar
Guo J, Li Z, Sandy AL, Li A. Method development for simultaneous analyses of multiple legacy and emerging organic chemicals in sediments. J Chromatogr A. 2014;1370:1–8.CrossRefGoogle Scholar
Guo T, LaBelle B, Petreas M, Park J-S. Mass spectrometric characterization of halogenated flame retardants. Rapid Commun Mass Spectrom. 2013;27:1437–49.CrossRefGoogle Scholar
Liu L-Y, Salamova A, Heb K, Hites RA. Analysis of polybrominated diphenyl ethers and emerging halogenated and organophosphate flame retardants in human hair and nails. J Chromatogr A. 2015;1406:251–7.CrossRefGoogle Scholar
Portolés T, Sales C, Gómara B, Sancho JV, Beltrán J, Herrero L, et al. Novel analytical approach for brominated flame retardants based on the use of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry with emphasis in highly brominated congeners. Anal Chem. 2015;87:9892–9.CrossRefGoogle Scholar
Suehring R, Barber JL, Wolschke H, Koetke D. Fingerprint analysis of brominated flame retardants and dechloranes in North Sea sediments. Environ Res. 2015;140:569–78.CrossRefGoogle Scholar
De la Torre A, Alonso MB, Martinez MA, Sanz P, Shen L, Reiner EJ, et al. Dechlorane-related compounds in Franciscana dolphin (Pontoporia blainvillei) from southeastern and southern coast of Brazil. Environ Sci Technol. 2012;46:12364–72.CrossRefGoogle Scholar
Munoz-Arnanz J, Roscales JL, Vicente A, Aguirre JI, Jimenez B. Dechlorane Plus in eggs of two gull species (Larus michahellis and Larus audouinii) from the southwestern Mediterranean Sea. Anal Bioanal Chem. 2012;404:2765–73.CrossRefGoogle Scholar
Papachlimitzou A, Barber J, Losada S, Bersuder P, Law R. A review of the analysis of novel brominated flame retardants. J Chromatogr A. 2012;1219:15–28.CrossRefGoogle Scholar
Wang P, Zhang Q, Zhang H, Wang T, Sun H, Zheng S, et al. Sources and environmental behaviors of Dechlorane Plus and related compounds – a review. Environ Int. 2016;88:206–20.CrossRefGoogle Scholar
Covaci A, Harrad S, Abdallah MA-E, Ali N, Law RJ, Herzke D, et al. Novel brominated flame retardants: a review of their analysis, environmental fate, and behavior. Environ Int. 2011;37:532–56.CrossRefGoogle Scholar
Lv S, Niu Y, Zhang J, Shao B, Du Z. Atmospheric pressure chemical ionization gas chromatography mass spectrometry for the analysis of selected emerging brominated flame retardants in foods. Sci Rep. 2017;7:1–8.CrossRefGoogle Scholar
Ballesteros-Gómez A, de Boer J, Leonards PEG. Novel analytical methods for flame retardants and plasticizers based on gas chromatography, comprehensive two-dimensional gas chromatography, and direct probe coupled to atmospheric pressure chemical ionization-high resolution time-of-flight-mass spectrometry. Anal Chem. 2013;85:9572–80.CrossRefGoogle Scholar
Geng D, Kukucka P, Jogsten IE. Analysis of brominated flame retardants and their derivatives by atmospheric pressure chemical ionization using gas chromatography coupled to tandem quadrupole mass spectrometry. Talanta. 2017;162:618–24.CrossRefGoogle Scholar
Sales C, Poma G, Malarvannan G, Portolés T, Beltrán J, Covaci A. Simultaneous determination of dechloranes, polybrominated diphenyl ethers and novel brominated flame retardants in food and serum. Anal Bioanal Chem. 2017;409:4507–15.CrossRefGoogle Scholar
Na G, Wei W, Zhou S, Gao H, Ma X, Ge L, et al. Distribution characteristics and indicator significance of dechloranes in multi-matrices at Ny-Ålesund in the Arctic. J Environ Sci (China). 2015;28:8–13.CrossRefGoogle Scholar
Suehring R, Byer J, Freese M, Pohlmann J-D, Wolschke H, Moeller A, et al. Brominated flame retardants and dechloranes in European and American eels from glass to silver life stages. Chemosphere. 2014;116:104–11.CrossRefGoogle Scholar
Ellison SLR, Williams A (eds) Eurachem/CITAC guide: quantifying uncertainty in analytical measurement. 3rd edn. 2012. Available from www.eurachem.org.
Magnusson B, Näykki T, Hovind H, Krysell M. Handbook for calculation of measurement uncertainty in environmental laboratories. Nordtest Report TR 537. 2003. www.nordtest.org
Gustavsson J, Ahrens L, Nguyena MA, Josefsson S, Wiberg K. Development and comparison of gas chromatography-mass spectrometry techniques for analysis of flame retardants. J Chromatogr A. 2017;1481:116–26.CrossRefGoogle Scholar
Baron E, Eljarrat E, Barcelo D. Analytical method for the determination of halogenated norbornene flame retardants in environmental and biota matrices by gas chromatography coupled to tandem mass spectrometry. J Chromatogr A. 2012;1248:154–60.CrossRefGoogle Scholar
Chen C-L, Tsai D-Y, Ding W-H. Optimization of matrix solid-phase dispersion for the determination of dechlorane compounds in marketed fish. Food Chem. 2014;164:286–92.CrossRefGoogle Scholar
Suehring R, Busch F, Fricke N, Kötke D, Wolschke H, Ebinghaus R. Distribution of brominated flame retardants and dechloranes between sediments and benthic fish – a comparison of a freshwater and marine habitat. Sci Total Environ. 2016;542:578–85.CrossRefGoogle Scholar
Suehring R, Moeller A, Freese M, Pohlmann J-D, Wolschke H, Sturm R, et al. Brominated flame retardants and dechloranes in eels from German rivers. Chemosphere. 2013;90:118–24.CrossRefGoogle Scholar
Baron E, Eljarrat E, Barcelo D. Gas chromatography/tandem mass spectrometry method for the simultaneous analysis of 19 brominated compounds in environmental and biological samples. Anal Bioanal Chem. 2014;406:7667–76.CrossRefGoogle Scholar
USP NF 39. USP NF 39 <736> mass spectrometry p. 5, table 1: Analytical Measurement Requirements (Category II)Google Scholar
Philipp R, Gonzales A, Cea AR. Traceable measurements for monitoring critical pollutants under the European Water Framework Directive (WFD-2000/60/EC). Joint Research Project ENV08 V6.0. 2015Google Scholar