Retrospective analysis by data processing tools for comprehensive two-dimensional gas chromatography coupled to high...

Data processing tools for non-target analysis using comprehensive two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HRTOFMS) were developed and applied to a sediment core in Tokyo Bay, focusing on chlorinated compounds in this study. The processing tools were classified in two different methods: (1) the consecutive use of mass defect filter followed by artificial neutral loss scan (MDF/artificial NLS) as a qualitative non-target screening method and (2) Entire Domain Combined Spectra Extraction and Integration Program (ComSpec) and two-dimensional peak sentinel (T-SEN) as a semi-quantitative target screening method. MDF/artificial NLS as a non-target screening approach revealed that PCBs, followed by octachlorodibenzo dioxin (OCDD), were the main chlorinated compounds present in all sediment layers. Furthermore, unknown peaks thought to be chlorinated compounds were found in increasing numbers, some in increasing amounts. T-SEN and ComSpec as a target screening approach were adapted for automatic semi-quantitative analysis showed that, in decreasing concentration order, PCBs, OCDD, and dichlorodiphenyltrichloroethane and its metabolites (DDEs, DDDs) were the main chlorinated pollutants in the sediments. The complementary use of both techniques allows us to extract significant chlorinated pollutants, including non-targeted compounds. This retrospective analysis by this approach performed well even on matrix-rich sediment samples and provided us an interesting insight of historical trends of pollution in Tokyo Bay.