Comparison and Evaluation of Isotope-Ratio Calculation Schemes for Compound-Specific Chlorine Isotope Analysis Using GC-EI-MS

TL;DR

This study compares isotope-ratio calculation schemes for compound-specific chlorine isotope analysis using GC-EI-MS, highlighting differences in precision and trueness, and questioning the binomial distribution assumption underlying current methods.

Contribution

It evaluates the accuracy of existing isotope-ratio calculation schemes and challenges the assumption of binomial distribution of chlorine isotopologues in CSIA-Cl.

Findings

Comparable precisions achieved by GC-IRMS and GC-qMS

Confirmed the trueness of analysis results

Questioned the binomial distribution hypothesis for isotopologue abundances

Abstract

A recent article reported a comparison study concerning compound-specific chlorine isotope analysis (CSIA-Cl) of organochlorines using gas chromatography- isotope ratio mass spectrometry (GC-IRMS) and gas chromatography-quadrupole mass spectrometry (GC-qMS). Comparable precisions between the two instruments were achieved and trueness of the analysis results was confirmed. The CSIA-Cl method using GC-qMS was originally developed by Sakaguchi-S\"oder et al.and further improved by several relevant studies,and has been used to evaluate organic contaminant attenuation in the environment. The essential principle of the method is to calculate the chlorine isotope ratio (37Cl/35Cl) by using the first pair of neighboring chlorine isotopologues (two-mass apart) of either the molecular ion or a fragmental ion of a target analyte, or using all the first isotopologue pairs of all molecular and fragmental ions. These isotope-ratio calculation schemes using chlorine isotopologue pair(s) were based on the binomial theorem and the prerequisite hypothesis that the measured abundances of chlorine isotopologues of individual analytes were binomially distributed. However, it is not true with the hypothesis.