Determination of Halogenated Flame Retardants Using Gas Chromatography with Atmospheric Pressure Chemical Ionization (APCI) and a High-Resolution Quadrupole Time-of-Flight Mass Spectrometer (HRqTOFMS)

A method to determine halogenated flame retardants was developed that utilizes gas chromatography with atmospheric chemical ionization (APCI) high-resolution quadrupole time-of-flight mass spectrometry (HRqTOFMS). The new GC-APCI-HRqTOFMS method was used to determine the presence of 65 halogenated flame retardants (HFRs) in the United Sates National Institute of Standards and Technology (NIST) organic contaminants in house dust standard reference material (SRM). The accuracy of the measurements was compared to the certified NIST value for polybrominated diphenyl ethers (PBDEs) and had an average accuracy for the 14 certified PBDEs of 109% with subpicogram detection limits (on column) from a single 1 μL injection with a run time of 18 min. SRM2585 extracts were also analyzed by GC electron ionization (EI) high-resolution mass spectrometry (HRMS), and there was an excellent correlation between the two data sets (R2 value of 0.996). The presence of 25 additional HFRs were also screened in the dust standard, and 10 were detected in concentrations above the limits of detection; these were p-TBX, PBBZ, PBT, PBEB, TDCPP, HBBZ, EHTBB, TBBPA, BEHTBP, and BTBPE. The results presented show that the proposed APCI-HRqTOFMS method was comparable and in many cases an improvement on the existing EI-HRMS method.