Chlorinated organic compounds in concrete as specific markers for chlorine gas exposure

Nurhazlina Hamzah; Karin Höjer Holmgren; Crister Åstot; Marcel J van der Schans; Leo de Reuver; Paula Vanninen

doi:10.1016/j.jhazmat.2023.132332

Chlorinated organic compounds in concrete as specific markers for chlorine gas exposure

J Hazard Mater. 2023 Oct 5:459:132332. doi: 10.1016/j.jhazmat.2023.132332. Epub 2023 Aug 16.

Authors

Nurhazlina Hamzah¹, Karin Höjer Holmgren², Crister Åstot², Marcel J van der Schans³, Leo de Reuver³, Paula Vanninen⁴

Affiliations

¹ Finnish Institute for Verification of the Chemical Weapons Convention (VERIFIN), Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland. Electronic address: nurhazlina.hamzah@helsinki.fi.
² The Swedish Defence Research Agency, FOI CBRN Defence and Security, SE-901 82 Umeå, Sweden.
³ TNO Defence, Safety and Security, Dep. CBRN Protection, Lange Kleiweg 137, 2288GJ Rijswijk, the Netherlands.
⁴ Finnish Institute for Verification of the Chemical Weapons Convention (VERIFIN), Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland.

PMID: 37598516
DOI: 10.1016/j.jhazmat.2023.132332

Abstract

The formation of chlorinated organic compounds in concrete debris exposed to reactive chlorine was studied to search for markers specific to chlorine gas exposure. Concrete materials of different origins were exposed to a range of species of reactive chlorine including bleach, humid and dry chlorine gas at different concentrations. Chlorinated organic compounds in concrete extracts were analysed by targeted gas and liquid chromatography-tandem mass spectrometry (GC-MS/MS and LC-MS/MS) and by non-targeted screening using the corresponding high-resolution techniques (GC-HRMS and LC-HRMS). Overall, different levels and species of chlorinated organic compounds namely chlorophenols, chlorobenzenes, chloromethoxyphenols, chloromethylbenzenes and chloral hydrate were identified in these chlorinated concrete extracts; two examples of diagnostic markers for neat chlorine exposure were trichloromethylbenzene and tetrachlorophenol. The old concrete samples from the 1930s and 1950s had the most chlorinated organic compounds after exposure to neat chlorine gas. Lignin or lignin degradation products were identified as probable candidates for phenolic precursor molecules in the concrete samples. Multivariate data analysis (OPLS-DA) shows distinct patterns for bleach and chlorine exposure. The chlorinated chemicals and specific markers for chlorine gas discovered in our research assist other laboratories in forensic investigations of chlorine gas attacks.

Keywords: Chlorinated organic compounds; Chlorine; Concrete of various ages and different origins; Gas Chromatography High-Resolution Mass Spectrometry (GC-HRMS); Liquid Chromatography High-Resolution Mass Spectrometry (LC-HRMS).