High-Resolution Mass Spectrometry Screening of Emerging Organophosphate Esters (OPEs) in Wild Fish: Occurrence, Species-Specific Difference, and Tissue-Specific Distribution

There is a dearth of information regarding the pollution status of emerging organophosphate esters (OPEs) in wild fish. Here, we optimized and validated a quick, easy, cheap, effective, rugged, and safe (QuEChERS) pretreatment method, which was further applied for target, suspect, and nontarget screening of OPEs in n = 48 samples of wild fishes from Taihu Lake (eastern China). This integrated technique allows us to fully identify 20 OPEs, and 9 out of them are emerging OPEs detected in wild fish for the first time. Importantly, some of the emerging OPEs, i.e., tris(2,4-di-tert-butylphenyl) phosphate (TDtBPP), 4-tert-butylphenyl diphenyl phosphate (BPDP), and 2-isopropylphenyl diphenyl phosphate (IPDP), exhibited greater or at least comparable contamination levels as compared to traditional ones. There were no statistically significant interspecies (n = 6) differences regarding OPE concentrations. However, we observed significant differences on OPE concentrations among different tissues of silver carp (Hypophthalmichthys molitrix), for which the intestine has the highest OPE mean concentration (46.5 ng/g wet weight (ww)), followed by the liver (20.1 ng/g ww) ≈ brain (20.0 ng/g ww) > gill (14.8 ng/g ww) > muscle (11.4 ng/g ww). An interesting exception is IPDP, which presents an unexpectedly high concentration in the brain (0.510 ng/g ww). Collectively, this study expands our understanding of OPE contamination in wild fish and clearly shows that emerging TDtBPP, IPDP, and BPDP could play an equally important role as traditional OPEs in contribution of OPE pollution in wild fish samples.