Quantification of short- and medium-chain chlorinated paraffins in environmental samples by gas chromatography quadrupole time-of-flight mass spectrometry

•Chlorinated paraffins (CPs) are complex mixtures of compounds and isomers.•CPs contain short-chain CPs (SCCPs) and medium-chain CPs (MCCPs).•SCCPs and MCCPs were analyzed using GC-NCI-qTOF-HRMS.•CPs were quantified, and their accurate masses and detection limits determined.•The developed method allows the analysis of samples from a range of matrices.

Chlorinated paraffins (CPs) are technical products produced and used in bulk for a number of purposes. However, the analysis of CPs is challenging, as they are complex mixtures of compounds and isomers. We herein report the development of an analytical method for the analysis of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) using quadrupole time-of-flight high-resolution mass spectrometry (GC-NCI-qTOF-HRMS). This method employs gas chromatography with a chemical ionization source working in negative mode. The linear relationship between chlorination and the CP total response factors was applied to quantify the CP content and the congener group distribution patterns. In a single injection, 24 SCCP formula groups and 24 MCCP formula groups were quantified. Extraction of accurate masses using qTOF-HRMS allowed the SCCPs and MCCPs to be distinguished, with interference from other chemicals (e.g., PCBs) being largely avoided. The SCCP and MCCP detection limits were 24–81 ng/mL and 27–170 ng/mL, respectively. Comparison of the obtained results with analytical results from gas chromatography coupled with electron capture negative ionization low-resolution mass spectrometry (GC-ECNI-LRMS) indicate that the developed technique is a more accurate and convenient method for the analysis of CPs in samples from a range of matrices.