Novel organophosphate esters and their transformation products in offshore sediment from Eastern China: Occurrence, temporal trend, and risk assessment

Offshore sediment serves as an important sink for traditional organophosphate esters (TOPEs) originating from terrestrial sources. However, the contamination characteristics of novel OPEs (NOPEs) and their hydrolyzed and hydroxylated transformation products (Di- and OH-OPEs) in marine sediment are still unknown. In this study, 34 OPE-associated contaminants were measured in six offshore sediment cores (71 samples) collected from Eastern China. The total concentrations of Σ₁₅TOPEs, Σ₃NOPEs, Σ₉Di-OPEs, and Σ₇OH-OPEs in surface sediments were 3.16-73.4, n.d.-16.3, 4.48-21.4, and 0.14-0.42 ng g^-1, respectively. NOPE compounds, such as tris(2,4-di-tert-butylphenyl) phosphate and its diester product, exhibited high contamination levels, primarily due to their high hydrophobicity and extensive industrial applications. Additionally, atmospheric transportation, along with wet and dry deposition and ocean currents, plays a crucial role in their distribution in offshore sediment. The location conditions and historical usage also influenced the vertical distributions of OPE-associated contaminants in sediment cores. Notably, a concentration peak of bis(2,4-di-tert-butylphenyl) phosphate (B2,4DtBPP) was dating back to 1940s, indicating the early usage of antioxidant tris(2,4-di-tert-butylphenyl) phosphite. Furthermore, a risk quotient (RQ) model was employed to assess the ecological risks posed by OPEs. Generally, the acute toxicity-based predicted no-effect concentrations for studied compounds were 1 to 2 orders of magnitude lower than those based on chronic toxicity. NOPEs and B2,4DtBPP exhibited high ecological risks, with maximum RQ values of 1570-4877 based on acute toxicity and 93.4-197 based on chronic toxicity. Notably, ΣRQ values for NOPEs were significantly higher than those of TOPEs (Mann-Whitney U test, p < 0.001), indicating their severe ecological risks in offshore sediment. Therefore, given the continuous input and considerable persistence of NOPEs in offshore sediment, their toxic effects and mechanisms warrant thorough investigation. This study provides the first evidence for the occurrence, temporal trends, and potential risks of NOPEs in marine sediment environment.