Analysis of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in air emission samples by GCHRMS: method development, validation and a real-case application.

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) are emerging dioxin-like pollutants formed during bromine-containing thermal processes, yet not harmonized analytical methods currently exist for their determination in atmospheric emissions. Most applications adapt PCDD/F protocols despite the distinct physicochemical behaviour of brominated analogues and their associated analytical challenges. Here, an improved GCHRMS method is presented for the determination of the thirteen commercially available 2,3,7,8-PBDD/F congeners in air emissions, providing an alternative sample preparation workflow avoiding dichloromethane during clean-up and fractionation. Key instrumental parameters -pulsed splitless injection, pulse conditions, inlet temperature, carrier gas flow and electron ionization energy- were optimized to enhance sensitivity across tetra- to octabrominated congeners. Sample preparation consisted of 20 h Soxhlet extraction with toluene, followed by a simplified multilayer silica column (without AgNO3) and an activated carbon fractionation, enabling a selective PBDE-PBDD/F separation through planarity-based retention. Method validation, following criteria adapted from EN 1948 and EPA 1613, demonstrated satisfactory analytical performance, including linearity over at least two orders of magnitude (relative response factor RSD ≤ 9 %), repeatability of 0.8-6.1 % in real emission matrices, accuracy ranging from -7.6 % to +17.4 %, and method quantification limits of 0.014-0.429 pg Nm-3. Application to an eleven-month industrial monitoring campaign confirmed method robustness under routine conditions and enabled congener-resolved PBDD/F profiling and provisional I-TEQ and WHO22-TEQ assessment. Overall, the present study reports a validated and integrated DCM-free analytical workflow for PBDD/F, providing a practical expansion of available strategies for future monitoring and standardisation efforts.