Congener-specific determination of brominated/chlorinated dioxins and related compounds by two-dimensional HPLC cleanup system

Abstract

The method enables congener-specific determination not only of polychlorinated dioxins but also of polybrominated diphenyl ethers (PBDEs), -biphenyls (PBBs), -dibenzo-p-dioxins (PBDDs) and -dibenzofurans (PBDFs) using two dimensional high performance liquid chromatograph (HPLC) with graphitized carbon and pyrenyl silica columns cleanup, and high resolution gas chromatograph with high resolution mass spectrometry (HRGC/HRMS) system. Additionally, the analytical method developed enables separation and quantification not only of PBDFs without co-elution from PBDEs but also of PBDE IUPAC No. 209. The reliable analysis of PBDE-209 was operated in parallel by the HRGC/HRMS and GC with tandem mass spectrometry, because the quantitative analysis of PBDE-209 is relatively difficult task due to liable physical properties and high molecular weight. Calibration curves from the peak areas of PBDEs, PBBs and PBDDs/DFs were linear with high correlation coefficients of more than 0.992 at the range from 2 to 1000 pg/μl (some congeners:10 to 1000 pg/μl). The relative standard deviations of PBDEs, PBBs and PBDDs/DFs by the peak areas were acceptable with a range of 2.7 to 11.2%, 2.0 to 11.7% and 5.9 to 12.5%, respectively. This analytical method could be applied to various matrices on pine needles as passive indicator and fly ash of international calibration study. Congener-specific determination of PBDEs, PBBs and PBDDs/DFs in pine needles was achieved in this study for the first time. Risk assessment by congener-specific data of brominated/chlorinated dioxins and related compounds was possible to carry out using this developed method. © 2006 The Japan Society for Analytical Chemistry.