Chloride-attachment atmospheric pressure photoionisation for the determination of short-chain chlorinated paraffins by gas chromatography-high-resolution mass spectrometry.

In this work, a new gas chromatography-high-resolution mass spectrometry (GC-HRMS) method based on atmospheric pressure photoionisation (APPI) has been developed for the accurate determination of short-chain chlorinated paraffins (SCCPs) as a reliable alternative to the established methods. To the best of our knowledge, this is the first time these compounds has been analysed by GC-MS using atmospheric pressure photoionisation (APPI). Efficient ionisation of SCCPs was achieved using the new GC-APPI source by the formation of [M+Cl] adduct ions in negative ion mode using dopant-assisted APPI with a mixture of acetone/CCl (3:1, v/v). Operating at a resolution of 70,000 FWHM (full width at half maximum) and monitoring the [M+Cl] adduct ions for each congener group, a selective determination of the SCCPs was achieved, avoiding isobaric interferences between homologue groups with different carbon chain length and chlorination degree. Moreover, the GC-APPI-HRMS response of each congener group was mainly influenced by its concentration and did not depend on the number of chlorine atoms in the molecule as occurs with the GC-MS methods based on the electron-capture negative ionisation (ECNI). Thus, the contribution of the different carbon and chlorine homologue groups in the SCCP mixtures was determined by the internal normalization method, and the quantification was performed independently of the chlorine content of the SCCP standard mixture employed. The developed GC-APPI-HRMS method offers some interesting advantages over the existing methods, particularly the possibility to quantify individual SCCP congener groups, the use of a simple calibration method for quantification, and an important time-saving in the data processing, especially over ECNI-based traditional methods. The GC-APPI-HRMS method allowed the determination of SCCPs at low concentration levels in fish samples with low method limits of detection (17-34 pg g wet weight for total SCCPs), good precision (RSD < 7%) and trueness (relative error < 8%) and can be proposed as a reliable alternative of the established methods for the determination of these pollutants in environmental samples.