Molecular insights into the formation and remobilization potential of nonextractable anthropogenic organohalogens in heterogeneous environmental matrices

Abstract

Anthropogenic organohalogens (AOHs) are toxic and persistent pollutants that occur ubiquitously in the environment. An unneglectable portion of them can convert into nonextractable residues (NER) in the natural solid substances. NER-AOHs are not detectable by conventional solvent-extraction, and will get remobilized through changes of surrounding environment. Consequently, the formation and fate of NER-AOHs should be investigated comprehensively. In this study, solvent extraction, sequential chemical degradation and thermochemolysis were applied on different sample matrices (sediments, soils and groundwater sludge, collected from industrial areas) to release extractable and nonextractable AOHs. Covalent linkages were observed most favorable for the hydrophilic-group-containing monocyclic aromatic AOHs (HiMcAr-AOHs) (e.g. halogenated phenols, benzoic acids and anilines) incorporating into the natural organic matter (NOM) as NER. Physical entrapment mainly contributed to the NER formation of hydrophobic monocyclic aromatic AOHs (HoMcAr-AOHs) and polycyclic aromatic AOHs (PcAr-AOHs). The hypothesized remobilization potential of these NER-AOHs follow the order HiMcAr-AOHs > HoMcAr-AOHs/ aliphatic AOHs > PcAr-AOHs. In addition, the NOM macromolecular structures of the studied samples were analyzed. Based on the derived results, a conceptual model of the formation mechanisms of NER-AOHs is proposed. This model provides basic molecular insights that are of high value for risk assessment and remediation of AOHs. © 2019 Elsevier B.V. All rights reserved.