Simultaneous determination of stable chlorine and bromine isotopic ratios for bromochlorinated trihalomethanes using GC-qMS

Bromochlorinated compounds are organic contaminants originating from different natural and anthropic sources and increasingly found in different environmental compartments. This work presents an online approach for compound specific stable isotope analysis of chlorine and bromine isotope ratios for bromochlorinated trihalomethanes using gas chromatography coupled to quadrupole mass spectrometry (GC-qMS).

An evaluation scheme was developed to simultaneously determine stable chlorine and bromine isotope ratios based on the mass spectral data of two target compounds: dibromochloromethane and dichlorobromomethane. The analytical technique was optimized by assessing the impact of different instrumental parameters, including dwell time, split ratios, and ionization energy.

Successively, static headspace samples containing the two target compounds at aqueous concentrations ranging from 0.1 mg/L to 5 mg/L were analyzed in order to test the precision and reproducibility of the proposed approach. The results showed a good precision under the optimized instrumental conditions, with relative standard deviations ranging between 0.05% and 0.5% for chlorine and bromine isotope analysis.

Finally, the method was tested in a source identification problem in which the simultaneous determination of chlorine and bromine stable isotope ratios allowed the clear distinction of dibromochloromethane from three different manufacturers.