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Compound-specific chlorine isotope analysis (CSIA-Cl) is a practicable andhigh-performance approach for quantification of transformation processes andpollution source apportionment of chlorinated organic compounds. This studydeveloped a CSIA-Cl method for perchlorethylene (PCE) and trichloroethylene(TCE) using gas chromatography-double focus magnetic-sector high resolutionmass spectrometry (GC-DFS-HRMS) with a bracketing injection mode. The achievedhighest precision for PCE was 0.021% (standard deviation of isotope ratios),and that for TCE was 0.025%. When one standard was used as the externalisotopic standard for another of the same analyte, the lowest standarddeviations of relative isotope-ratio variations ({\delta}37Cl') between the twocorresponding standards were 0.064% and 0.080% for PCE and TCE, respectively.As a result, the critical {\delta}37Cl' for differentiating two isotope ratiosare 0.26% and 0.32% for PCE and TCE, respectively, which are comparable withthose in some reported studies using GC-quadrupole MS (GC-qMS). The lower limitof detection for CSIA-Cl of PCE was 0.1 ug/mL (0.1 ng on column), and that forTCE was determined to be 1.0 ug/mL (1.0 ng on column). Two isotope ratiocalculation schemes, i.e., a scheme using complete molecular-ion isotopologuesand another one using a pair of neighboring isotopologues, were evaluated interms of precision and accuracy. The complete-isotopologue scheme showedevidently higher precision and was deduced to be more competent to reflecttrueness in comparison with the isotopologue-pair scheme. The CSIA-Cl methoddeveloped in this study will be conducive to future studies concerningtransformation processes and source apportionment of PCE and TCE, and light theways to method development of CSIA-Cl for more organochlorines.

Compound-Specific Chlorine Isotope Analysis of Organochlorines Using Gas  Chromatography-Double Focus Magnetic-Sector High Resolution Mass Spectrometry