Halogenated organic compounds in wastewater are persistent and bioaccumulative contaminants of great concern, but few are known at the molecular level. Herein, we focus on nontarget screening of halogenated dissolved organic matter (DOM) in highly concentrated organic matrices of waste leachates and their concentrates. Solid-phase extraction (SPE) was optimized before capturing halogenated signatures via HaloSeeker 2.0 software on mining full-scan high-resolution mass spectrometry (HRMS) fingerprints. This study identified 438 Cl-/Br-containing DOM formulas in 21 leachates and membrane concentrates. Among them, 334 formulas were achieved via SPE with mixed-sorbent cartridges (mixed-SPE), surpassing the 164 formulas achieved through Bond Elut PPL cartridges (PPL-SPE). Herein, only four samples identified via PPL-SPE exhibited a resolution of >50% for extracted Cl-/Br-containing DOM by either SPE. The halogenated DOM constituted 6.87% of the total DOM mass features. Nevertheless, more abundant adsorbable organic halogens deciphered waste leachates and highly concentrated waste streams as reservoirs for halogenated contaminants. Remarkably, 75.7-98.1% of Cl-/Br-containing DOM in primary membrane concentrates remained stable through the secondary membrane treatment, indicating the persistence of these unknown contaminants even post-treatment.
Keywords: dissolved organic matter; halogenated organic compounds; leachate; membrane concentrate; nontarget analysis; solid waste.