Target and Nontarget Analysis of Organophosphorus Flame Retardants and Plasticizers in a River Impacted by Industrial Activity in Eastern China

Industrial activities are a major source of organophosphorus flame retardants (OPFRs) and plasticizers in aquatic environments. This study investigated the distribution of 40 OPFRs in a river impacted by major industrial manufacturing plants in Eastern China by target analysis. Nontarget analysis using high-resolution mass spectrometry was further employed to identify novel organophosphorus compounds (NOPs). Thirty-four OPFRs were detected in river water samples, with total concentrations of 62.9-1.06 × 10³ ng/L (median: 455 ng/L). Triphenylphosphine oxide and diphenyl phosphoric acid were ubiquitously detected up to 620 and 127 ng/L, respectively. Among 26 identified NOPs, 17 were reported for the first time in the environment, including 14 novel organophosphate esters (especially 4 heterocycles and 3 oligomers), 2 organophosphites, and an organophosphonate. Bis(2,4-di-<i>tert</i>-butylphenyl) hydrogen phosphate and 2,2-dimethylpropoxy(propyl)phosphinic acid with high predicted persistence or toxicity were widely detected, with semiquantified concentrations up to 990 and 1.0 × 10³ ng/L, respectively. Structurally similar organophosphorus heterocycles exhibited consistent variation trends, suggesting a common emission source. Estimated annual river discharges to the sea were 20.6-37.0 kg/yr for OPFRs and 30.8-161 kg/yr for NOPs. These findings indicate that industrial activities contribute OPFRs and NOPs to the river catchment and its estuary, posing ecological risks to both terrestrial and marine environments.