Occurrence and transformation of unknown organochlorines in the wastewater treatment plant using specific Fragment-Based method with LC Q-TOF MS.

Wastewater treatment plants (WWTPs) are important point sources of organochlorines in surface waters. However, comprehensive molecular-level understanding of the occurrence and transformation of organochlorines in WWTPs remains elusive. In this study, a specific fragment-based screening method with SWATH of LC Q-TOF MS was established to better understand the molecular composition of organochlorines. This method effectively excludes the non-chlorinated signals and provides multi-dimensional information (e.g., retention time, precursor ion mass, product ions, and molecular formula) with one injection to identify the possible structures of organochlorines. Eighty-seven organochlorines were successfully screened in practical wastewater samples, where 8 chlorinated sulfonic acids, 4 chlorophenols, 4 chlorinated benzenediols, and 6 chlorinated benzoic acids were further (tentatively) identified. Relative abundance of organochlorines showed that their occurrence was associated with the treatment units. In particular, anaerobic biological and NaClO treatment units contributed to the formation of chlorinated by-products. Most chlorinated by-products were substituted with more chlorine atoms than organochlorines from the influent. Furthermore, the relative abundance indicated that the fate of organochlorines were related to their structures. Chlorinated benzene sulfonic acids would be removed by adsorption on activated sludge. Most chlorinated benzoic acids were refractory, but some were likely to be chlorinated during the anaerobic process. Chlorophenols and chlorinated benzenediols might undergo chlorination, dealkylation/C-O bond breakage, and bromination. Our study offers a new tool to gain molecular information on organochlorines in complex environmental samples and highlights the importance of molecular structures when evaluating the fate of organochlorines and managing effluent discharge to surrounding waters.