Quantification of Brominated Flame Retardants in Synthetic Polymers via Direct Mass Spectrometric Analysis

Abstract

Brominated flame retardants (BFRs) are persistent organic pollutants commonly encountered in plastics. Herein, we report on the quantification of BFRs directly from plastic samples via direct insertion probe mass spectrometry (DIP-MS). The study was conducted using model polymer samples comprising either acrylonitrile butadiene styrene copolymer (ABS) or high impact polystyrene (HIPS) and a BFR, namely decabromodiphenyl ether (decaBDE), hexabromocyclododecane (HBCD), or tetrabromobisphenol A (TBBPA). DIP-MS enabled direct quantification of decaBDE and TBBPA from both ABS and HIPS matrices. A linear correlation between BFR signal intensity and bromine (Br) content of the samples, as determined by X-ray fluorescence, was established over a Br concentration range of 0–7 wt %, or even higher. While DIP-MS showed potential for HBCD analysis as well, its effectiveness for quantitative HBCD determination remains partly uncertain due to the observed reactivity of HBCD during sample preparation. The detection limits for all studied BFRs were below 500 mg Br/kg. Additionally, the study shed light on matrix effects related to additive analysis by DIP-MS, revealing that the polymer and other additives can affect BFR volatilization and reactivity. Overall, DIP-MS demonstrated significant potential for the rapid quantification of BFRs from plastic samples with minimal sample preparation, which is imperative for promoting more efficient plastic recycling.