Chlorine and bromine isotope fractionation of halogenated organic pollutants on gas chromatography columns

- On-column Cl/Br isotope fractionation of 35 HOPs was explored with GC-DFS-HRMS.
- Inverse, normal and unobservable Cl/Br isotope fractionations were found depending on compound.
- A modified two-film model was used to elucidate the on-column Cl/Br isotope fractionation.
- Solutions were proposed to improve precision and accuracy of CSIA-Cl/Br using GC-MS techniques.

Compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) has become a powerful approach to investigate degradation pathways and apportion sources of halogenated organic pollutants (HOPs) in the environment. CSIA-Cl/Br is usually conducted by gas chromatography-mass spectrometry (GC-MS), which could be negatively impacted by isotope fractionation on GC columns. In this study, on-column Cl/Br isotope fractionation of 31 organochlorines and 4 organobromines was explored using GC-double focus magnetic-sector high resolution MS (GC-DFS-HRMS). Twenty-nine HOPs exhibited inverse Cl/Br isotope fractionation for which the heavier isotopologues eluted faster than the lighter ones on GC columns, and two polychlorinated biphenyls (PCB-138 and PCB-153) showed normal isotope fractionation, whereas the rest four HOPs did not show observable isotope fractionation. The isotope fractionation extents varied from −13.0‰ to 73.1‰. Mechanisms of the on-column Cl/Br isotope fractionation were tentatively elucidated with a modified two-film model. The results demonstrate that integrating peak area as complete as possible for separable chromatographic peaks and integrating the middle retention-time segments for the inseparable peaks are helpful to improve precision and accuracy of the CSIA-Cl/Br data. The findings of this study will shed light on development of CSIA-Cl/Br methods with respect to improving precision and accuracy.