Discovering Novel Organophosphorus Compounds in Wastewater Treatment Plant Effluents through Suspect Screening and Nontarget Analysis

Abstract

Limited knowledge on the structure of emerging organophosphorus compounds (OPCs) hampers our comprehensive understanding of their environmental occurrence and potential risks. Through suspect and nontarget screening, combining data-dependent acquisition, data-independent acquisition, and parallel reaction monitoring modes, we identified 60 OPCs (17 traditional and 43 emerging compounds) in effluents of 14 wastewater treatment plants (WWTPs) in Beijing and Qinghai, China. These OPCs comprise 26 organophosphate triesters, 17 organophosphate diesters, 6 organophosphonates, 7 organothiophosphate esters, and 4 other OPCs. Notably, 14 suspect OPCs were newly identified in WWTP effluents, and 16 nontarget OPCs were newly discovered in environmental matrices. Specifically, the cyclic phosphonate, (5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)­methyl dimethyl phosphonate P-oxide (PMMMPn), consistently appeared in all WWTP effluents, with semiquantitative concentrations ranging from 44.4 to 282 ng/L. Its analogue, di-PMMMPn, presented in 93% of wastewater samples. Compositional differences between the WWTP effluents of two cities were mainly attributed to emerging OPCs. Hazard and ecological risk assessment underscored the substantial contribution of chlorinated organophosphate esters and organothiophosphate esters to overall risks of OPCs in WWTP effluents. This study provides the most comprehensive OPC profiles in WWTP effluents to date, highlighting the need for further research on their occurrence, fate, and risks, particularly for chlorinated OPCs.

Integration of Nontarget Screening and QSPR Models to Identify Novel Organophosphate Esters of High Priority in Aquatic Environment

“…The ranges of LODs of the standards were 0.002–2.00 ng/L, 0.001–0.09 ng/g, 0.001–0.82 ng/g, and for LOQs, they were 0.006–7.00 ng/L, 0.003–0.32 ng/g, 0.003–3.00 ng/g, respectively (Table S7). The newly identified candidates were semiquantified using the commercially available standards of structurally similar OPEs (Table S8), ,,, which might cause some level of uncertainty of the semiquantified data in this study.…”