Cracked and shucked: GC-APCI-IMS-HRMS facilitates identification of unknown halogenated organic chemicals in French marine bivalves

Abstract

High resolution mass spectrometry (HRMS)-based non-target analysis coupled with ion mobility spectrometry (IMS) is gaining momentum due to its ability to provide complementary information which can be useful in the identification of unknown organic chemicals in support of efforts in unraveling the complexity of the chemical exposome. The chemical exposome in the marine environment, though not as well studied as its freshwater counterparts, is not foreign to chemical diversity specially when it comes to potentially bioaccumulative and bioactive polyhalogenated organic contaminants and natural products. In this work we present in detail how we utilized IMS-HRMS coupled with gas chromatographic separation and atmospheric pressure chemical ionization (APCI) to annotate polyhalogenated organic chemicals in French bivalves collected from 25 sites along the French coasts. We describe how we used open cheminformatic tools to exploit isotopologue patterns, isotope ratios, Kendrick mass defect (Cl scale), and collisional cross section (CCS), in order to annotate 157 halogenated features (level 1: 54, level 2: 47, level 3: 50, and level 4: 6). Grouping the features into 11 compound classes was facilitated by a KMD vs CCS plot which showed co-clustering of potentially structurally-related compounds. The features were semi-quantified to gain insight into the distribution of these halogenated features along the French coast, ultimately allowing us to differentiate between sites that are more anthropologically impacted versus sites that are potentially biodiverse.