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Analytical and Bioanalytical Chemistry

, Volume 410, Issue 4, pp 1375–1387 | Cite as

Determination of halogenated flame retardants by GC-API-MS/MS and GC-EI-MS: a multi-compound multi-matrix method

  • Frank Neugebauer
  • Annekatrin Dreyer
  • Nina Lohmann
  • Jan Koschorreck
Research Paper

Abstract

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%.

Graphical abstract

A new approach to HFR analysis in multiple environmental matrices

Keywords

Dechlorane Plus Brominated flame retardants nBFR German environment specimen bank Atmospheric pressure ionization 

Notes

Acknowledgments

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.

Supplementary material

216_2017_784_MOESM1_ESM.pdf (2.2 mb)
ESM 1 (PDF 2.24 MB)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  • Frank Neugebauer
    • 1
  • Annekatrin Dreyer
    • 2
  • Nina Lohmann
    • 1
  • Jan Koschorreck
    • 3
  1. 1.Eurofins GfA Lab Service GmbHHamburgGermany
  2. 2.Eurofins GfA GmbH, Air MonitoringHamburgGermany
  3. 3.German Environment AgencyBerlinGermany

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