Improved GC/ECNI-MS sensitivity of decabromodiphenyl ether determination on 30 m columns by increasing the carrier gas flow after a modified gel permeation chromatographic cleanup protocol employing cyclohexane/ethyl acetate as eluent

Abstract

BDE-209 is the predominant constituent of the commercial mixture decabromodiphenyl ether which is used as brominated flame retardant (BFR). Owing to difficulties associated with the high mass (thermal instability and low vapour pressure), short GC columns (≤15 m) have been suggested for its analysis while longer columns (30–50 m) are suggested for other polybrominated diphenyl ether (PBDE) congeners. To overcome this considerable expenditure in the analysis of PBDEs, we aimed at increasing the sensitivity of BDE-209 analysis by gas chromatography coupled with electron-capture negative ion mass spectrometry (GC/ECNI-MS) on a 30 m column. The chromatographic performance of BDE-209 on the 30 m GC column was improved by increasing the carrier gas flow from initially 1.2 mL min⁻¹ to 5 or 10 mL min⁻¹ after the last octabromo diphenyl ether (Br₈DE) congener was eluted. With this high carrier gas flow, the column residence time of BDE-209 was shortened by ∼25%, the peak height was increased and, consequently, the limit of detection by GC/ECNI-MS in selected ion monitoring (SIM) mode was improved. When this high-flow GC/ECNI-MS-SIM method was applied to a sediment sample, we realized that gel permeation chromatography (GPC) – used for the removal of lipids and/or sulphur – provided low recovery rates for BDE-209. The large molecule BDE-209 eluted late and only 50% was recovered by our previous standard protocol for polyhalogenated compounds. Application of a modified GPC procedure with a longer collection time increased the recovery of BDE-209 in the GPC step to ∼90%.

Keywords:

• Decabromodiphenyl ether
• High-flow gas chromatography
• GC/ECNI-MS
• Gel permeation chromatography

Acknowledgements

The authors greatly acknowledge Gregg Tomy (Freshwater Institute, Winnipeg, Canada) for the donation of the technical PBDE mixtures used in this work. We also thank Steffen Hägele (Institut für Siedlungsbau, Universität Stuttgart, Germany) for the donation of the sediment sample. Last but not least, we are grateful to the Deutsche Forschungsgemeinschaft (DFG) for financial support (VE 164/17-1).