Establishment and Application of the Co-analysis Method of PBDD/Fs and PCDD/Fs with Isotope Dilution High Resolution Gas Chromatography-High Resolution Mass Spectrometry in Ambient Air Samples

It has been known that the polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) share similar or even higher toxicity and bio-accumulativity with polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs). In this study, the co-analysis method of PBDD/Fs and PCDD/Fs with isotope dilution HRGC-HRMS was built based on the U.S. EPA Method 1613 and TO-9A. The samples were extracted and cleaned through acid silica gel bed, multi-layer silica gel column, and Florisil column, respectively. Eight 2,3,7,8-PBDD/Fs congeners and 17 congeners of 2,3,7,8-PCDD/Fs were quantified. The HRGC-HRMS conditions for PBDD/Fs were: EI+ and SIM model with resolution ≥ 10000, electron emission energy of 50 eV, and filament current of 0.75 mA; DB-5 MS fused silica capillary column (30 m × 0.25 mm i.d., 0.1 μm) was used and the temperatures for injection, ion source, and transfer line were 250 °C, 250 °C, and 305 °C, respectively. The carrier gas was helium (1.0 ml min−1). The results showed that the relative standard deviations (RSDs) of parallel blank samples were ≤ 10.3% and the recoveries of PBDD/Fs and PCDD/Fs were in the range of 73%–112%. The average quantified values of the standard reference sample were in accordance with the certified values and the RSDs were ≤ 12.0%. The method detection limits were 0.25–1.5 pg μl−1 for PBDD/Fs and 1.5–5 pg μl−1 for PCDD/Fs. The concentrations of PBDD/Fs and PCDD/Fs were 1.01–2.43 pg per m3 and 6.19–10.8 pg per m3 for particulate samples, and 0.036–0.801 pg per m3 and 1.37–12.1 pg per m3 for gaseous samples of certain area, respectively. Compared with other areas in the world, the atmospheric dioxins pollution of the sampling area was at high level.