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

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 for HFR, 20 pg injection for DBDPE, 7-36 pg injection 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 for HFR (DBDPE: 1000 pg sample) and 1200-6000 pg sample 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.

Validation Including Uncertainty Estimation of a GC–MS/MS Method for Determination of Selected Halogenated Priority Substances in Fish Using Rapid and Efficient Lipid Removing Sample Preparation

“…In the work dealing with determination of OC pesticides in meat employing ASE, mini-silica column purification and GC–ECD analysis, Dimitrova et al [29] obtained for hexachlorobenzene and HCH isomers expanded uncertainties in the range of 14.6%–17.9%. In the currently published study [30] concerning the determination of halogenated flame retardants by GC–API-MS/MS and GC–EI-MS after ASE and multi column clean-up, the values of expanded measurement uncertainties for the PBDEs of our interest in fish fillet were below 50%.…”

(Persistent) Organic pollutants in Germany: results from a pilot study within the 2015 moss survey

“…PBDE and HFR: Samples were analysed according to a method described by Neugebauer et al [ 36 ]. Briefly, nineteen mass-labelled standards were added to each sample of about 4 g dried moss prior to accelerated solvent extraction with hexane:dichloromethane 1:1 (v:v).…”

“…Except for the PBDE/HFR analysis, all analytical procedures were accredited. The method for the analysis of PBDE and HFR was extensively validated [ 36 ]. Certified reference material (EDF2525, T665QC) or similarly materials of known target analyte concentrations as well as blank samples were analysed to check the analytical performance.…”

Chemicals of emerging concern in marine specimens of the German Environmental Specimen Bank

“…Chemical analysis and quality assurance/quality control are outlined in the Additional file 1 and in Neugebauer et al [53] (FR), Rüdel et al [54,55] (PFAS) and Radermacher et al [56] (cVMS).…”

“…In brief, for FR analyses samples of blue mussels and eelpout filet were extracted by accelerated solvent extraction (ASE) with dichloromethane: hexane followed by a multi-column clean-up and quantification based on API-GC-MS/MS in the case of emerging flame retardants and GC-MS/MS in the case of PBDE. The limits of quantification (LOQs) for all compounds were roughly in the range of 0.00004-0.139 µg kg −1 wet weight (ww) depending on substance and matrix (Additional file 1: Table S1-S6, details also found in Neugebauer et al [53]).…”