Influence of watershed characteristics and human activities on the occurrence of organophosphate esters related to dissolved organic matter in estuarine surface water

Organophosphate esters (OPEs) are widespread in aquatic environments and pose potential threats to ecosystem and human health. Here, we profiled OPEs in surface water samples of heavily urbanized estuaries in eastern China and investigated the influence of watershed characteristics and human activities on the spatial distribution of OPEs related to dissolved organic matter (DOM). The total OPE concentration ranged from 22.3 to 1201 ng/L, with a mean of 162.6 ± 179.8 ng/L. Chlorinated OPEs were the predominant contaminant group, accounting for 27.4–99.6 % of the total OPE concentration. Tris(2-chloroisopropyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, and tributyl phosphate were the dominant compounds, with mean concentrations of 111.2 ± 176.0 ng/L, 22.6 ± 21.5 ng/L, and 14.8 ± 14.9 ng/L, respectively. Variable OPE levels were observed in various functional areas, with significantly higher concentrations in industrial areas than in other areas. Potential source analysis revealed that sewage treatment plant effluents and industrial activities were the primary OPE sources. The total OPE concentrations were negatively correlated to the mean slope, plan curvature, and elevation, indicating that watershed characteristics play a role in the occurrence of OPEs. Individual OPEs (triisobutyl phosphate, tris(2-butoxyethyl) phosphate, tris(2-chloroethyl) phosphate, and tricresyl phosphate) and Σalkyl-OPEs were positively correlated to the night light index or population density, suggesting a significant contribution of human activity to OPE pollution. The co-occurrence of OPEs and DOM was also observed, and the fluorescence indices of DOM were found to be possible indicators for tracing OPEs. These findings can elucidate the potential OPE dynamics in response to DOM in urbanized estuarine water environments with intensive human activities.