Chlorine isotope analysis of polychlorinated organic pollutants using gas chromatography-high resolution mass spectrometry and evaluation of isotope ratio calculation schemes by experiment and numerical simulation

Abstract

Compound-specific isotope analysis of chlorine (CSIA-Cl) is a practicable and high-performance approach for revelation of transformation processes and source identification of chlorinated organic pollutants. This study conducted CSIA-Cl for typical polychlorinated organic pollutants using gas chromatography-high resolution mass spectrometry (GCHRMS) with an alternate injection mode using perchloroethylene (PCE) and trichloroethylene (TCE) as model analytes. PCE and TCE standards from two manufacturers were employed for method development, and chlorine isotope ratio calculation schemes were evaluated by experiment and numerical simulation. The achieved precision (standard deviation of isotope ratios) was up to 0.21‰ for PCE and 0.43‰ for TCE. The limits of detection for CSIA-Cl of were 0.05 μg/mL (0.05 ng on column), and the linearities were 0.05–1 μg/mL. Two isotope ratio calculation schemes, i.e., one using complete molecular isotopologues and another using the first pair of neighboring chlorine isotopologues of each analyte, were evaluated in terms of accuracy and precision. The complete-isotopologue scheme showed evidently higher precision and was more competent to reflect trueness than the isotopologue-pair scheme and the two schemes could present completely different outcomes. The method has been successfully applied to PCE and TCE reagents from different suppliers, a trichloromethane reagent, and a plastic material. The relative isotope ratio variations (Δ37Cl) of PCE and TCE in the reagents and plastic material were from −1.84±0.7‰ to 15.12±0.85‰. The analytes from different sources could mostly be discerned from each other by chlorine isotope ratios. This study will be conducive to transformation process elucidation and source identification of for PCE and TCE, and facilitate CSIA-Cl using GC–MS for more polychlorinated organic pollutants, particularly in selection and optimization of isotope ratio calculation schemes.