Comparative evaluation of liquid chromatography–mass spectrometry versus gas chromatography–mass spectrometry for the determination of hexabromocyclododecanes and their degradation products in indoor dust

Domestic and office dust samples (n = 37) were analyzed for hexabromocyclododecanes (HBCDs) using gas chromatography–electron-capture negative ionization–mass spectrometry (GC–ECNI/MS) and liquid chromatography–electrospray tandem mass spectrometry (LC–ESI/MS/MS). To determine the best method to quantify HBCDs using GC–ECNI/MS, BDE 128 was used as internal standard (I.S.) in all samples, while 13C-labeled α-HBCD was used as I.S. in some samples. Total HBCD concentrations (sum of α-, β-, and γ-HBCD diastereomers) were calculated using response factors (RFs) for α- and γ-HBCD as individual diastereomers and using an average RF for both diastereomers. Statistical comparison showed that concentrations obtained via GC–ECNI/MS were statistically indistinguishable (p > 0.05) from those obtained using LC–ESI/MS/MS. The closest match between the two techniques was obtained using [13C]α-HBCD as I.S. and the average RF for α- and γ-HBCDs. Excellent linear correlations (Pearson coefficient values r > 0.9) were obtained between the GC–ECNI/MS and LC–ESI/MS/MS results, with slopes ranging from 0.76 to 1.36. Pentabromocyclododecenes (four isomers) and tetrabromocyclododecadienes (two isomers) were detected in the studied samples and were identified as degradation products of HBCDs after separation from the parent compound on the basis of both retention time and mass spectrum. This finding suggests that the elimination of HBr is the major degradation pathway for HBCDs in dust.