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-tert-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.