As prevalent emerging contaminants, organophosphate esters (OPEs) are widely detected in aquatic ecosystems. However, few studies have systematically compared their bioaccumulation and trophodynamics across different aquatic food webs. In this study, a total of 34 species (n = 498) were collected from Liaodong Bay (LDB) and Songhua River (SHR). Tri-n-propyl phosphate (TPP) and tris (2-chloroethyl) phosphate (TCEP) were the predominant OPEs in the organisms from LDB and SHR, respectively, with median concentrations of 147 and 266 ng/g lipid weight, lw. Low bioaccumulation was observed for 8 OPEs in LDB because their logarithmic bioaccumulation factors (log BAFs) were all below 3.7. In SHR, phytoplankton exhibited the strongest accumulation capacity for most OPEs, with the exception of TCEP. Overall, most OPEs presented higher bioaccumulation potential in freshwater food webs than in marine ones. TCEP and tris(2-ethylhexyl) phosphate (TEHP) had the highest biota-sediment accumulation factor (BSAF) in SHR (87.0) and LDB (248), respectively. A hump-shaped relationship between log Kow and log BAF suggested that OPEs with moderate hydrophobicity were more susceptible to bioaccumulation. Eight OPEs underwent biodilution in LDB; only TCEP displayed distinct biomagnification (trophic magnification factor = 1.75) in SHR, whereas other congeners showed biodilution. Salinity, pH and dissolved organic carbon exerted distinct effects on the bioaccumulation and trophodynamics of different OPEs. TCEP in most organisms in SHR may pose potential cancer risk, with the incremental lifetime cancer risk ranging from 10–6 to 10–4. This finding provides reliable field data and scientific support for differentiated ecological risk control of OPEs in diverse aquatic environments.
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