Nontarget analysis and comprehensive characterization of halogenated organic pollutants by GC-Q-Orbitrap-HRMS in association with chromatogram segmentation and Cl/Br-specific screening algorithms

Caiming Tang; Guangshi Chen; Yutao Liang; Jianbo Liao; Hui Lin; Chenchen Huang; Yanhong Zeng; Xiaojun Luo; Xianzhi Peng; Bixian Mai

doi:10.1016/j.aca.2022.340171

Nontarget analysis and comprehensive characterization of halogenated organic pollutants by GC-Q-Orbitrap-HRMS in association with chromatogram segmentation and Cl/Br-specific screening algorithms

Anal Chim Acta. 2022 Aug 22:1222:340171. doi: 10.1016/j.aca.2022.340171. Epub 2022 Jul 16.

Authors

Affiliations

¹ Laboratory of Advanced Analytical Chemistry and Detection Technology, Research Center for Eco-Environmental Engineering, Dongguan University of Technology, Dongguan, 523808, China; State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China. Electronic address: CaimingTang@dgut.edu.cn.
² State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China.
³ Laboratory of Advanced Analytical Chemistry and Detection Technology, Research Center for Eco-Environmental Engineering, Dongguan University of Technology, Dongguan, 523808, China.
⁴ State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China. Electronic address: zengyh@gig.ac.cn.

PMID: 35934429
DOI: 10.1016/j.aca.2022.340171

Abstract

Nontarget analysis enables high-efficiency screening and identification of halogenated organic pollutants (HOPs) in complex matrices irrespective of lacking authentic standards, particularly for novel and emerging species, thereby realizing comprehensive component characterization of HOPs. Notwithstanding, nontarget analysis and comprehensive characterization of HOPs remain on the way to improvement. In this study, we implemented nontarget analysis of HOPs in fly ash, egg and sediment using gas chromatography quadrupole-orbitrap high-resolution mass spectrometry with the aid of chromatogram segmentation and Cl/Br-specific screening algorithms, and further performed comprehensive characterization of components and distribution of HOPs. In total, 122 HOP formulas were identified and tentatively assigned with structures, of which 28 were found in ≥ two matrices. Taking isomers into account, in total 1059 HOP congeners were found. Based on the identification and semiquantification results, the chemical components and concentration profiles of HOPs were preliminarily clarified, and accordingly the overall pollution signatures of HOPs were sketched. The total concentrations of HOPs in the fly ash, egg and sediment were 4.7, 41.2 and 750.8 μg g^-1, respectively. Organochlorines were the most abundant among the categories classified by halogen types, and halogenated benzenes, halogenated dioxins, halogenated biphenyls/terphenyls and halogenated polycyclic aromatic hydrocarbons (H-PAHs) were the predominant of the structurally classified categories. Moreover, dozens of formulas of novel/little-known HOPs such as mix-chlorinated/brominated PAHs with ≥4 aromatic rings and polychlorinated terphenyls were identified. This study presents an accurate and high-performance nontarget analysis method for HOPs in complex matrices, and yields new cognitions on the pollution status of HOPs from an overall perspective.

Keywords: Cl/Br-specific screening algorithms; Comprehensive chemical characterization; Gas chromatography high-Resolution mass spectrometry; Halogenated organic pollutants; Nontarget analysis.

MeSH terms

Algorithms
Coal Ash / analysis
Environmental Pollutants* / analysis
Gas Chromatography-Mass Spectrometry / methods
Polycyclic Aromatic Hydrocarbons* / analysis

Substances

Coal Ash
Environmental Pollutants
Polycyclic Aromatic Hydrocarbons