| The analysis methods of 7 typical organophosphate flame retardants(OPEs)including tri-n-butyl phosphate(TnBP),tri(2-chloroethyl)phosphate(TCEP),trichloropropyl phosphate(TCPP),tridichloropropyl phosphate(TDCPP),triphenyl phosphate(TPhP),tributoxyethyl phosphate(TBEP),tris(2-ethylhexyl)phosphate(TEHP)in invarious tissues(muscle,sputum,liver,kidney)of fish were developed.Different species of fish in the Minjiang River Basin were sampled and their OPEs were quantitatively analyzed.In addition,the toxicokinetics of OPEs in Koi were studied by laboratory simulation.The main results are as follows:(1)Ultrasonic extraction-freeze filtration degreasing-column chromatography separation and purification-gas chromatography-mass spectrometry analysis of organophosphates in fish tissues was established and optimized with good quality control.The recoveries of TDCPP-d15 and TPhP-d15 in fish samples were 71.6%~85.2%and 75.3%~90.2%,respectively.The recoveries of TDCPP-d15 and TPhP-d15in water samples were 89.1%~104.1%and 85.3%~106.2%,respectively.The instrument precision is 8.0%~9.0%,and the detection limit is 0.07 ng~0.41 ng.The correlation coefficients(r)of the standard curves of the seven OPEs are all above0.99.(2)Different kinds of fish with different size in the Minjiang River Basin were collected and dissected into four tissues,namely,sputum,muscle,kidney and liver.Their OPEs contents were determined.The trend of total concentration of seven organophosphates(Σ7OPEs)in fish tissues was found to be:liver(1552.3~7090.9ng/g dw,mean of 2909.8 ng/g dw)>kidney(1842.1 ng/g dw~3134.3 ng/g dw,2625.8 ng/g dw)>sputum(1314.7~4447.6 ng/g dw,2263.85 Ng/g dw)>muscle(438.5 ng/g dw~1154.2 ng/g dw,602.9 ng/g dw).Except that TPhP(254.8 ng/g dw,accounting for 42.3%of 7OPEs)is the main pollutant in fish meat,TBEP is the main pollutant in other organs.The proportion of TPhP inΣ7OPEs in each organ was:liver(46%)>sputum(39.3%)>kidney(32.5%).The highest content of alkyl phosphate was found in the liver,while the highest content of chlorophosphate in the kidneys and the highest content of aryl phosphate in the sputum.(3)A 42-days toxicokinetic experiment was performed to determine the enrichment and discharge of seven OPEs in different tissues of Koi(muscle,sputum,kidney,and liver).The results showed that the significant bioaccumulation effect was only found for TPhP,with the bioconcentration factor(BCF)of 8100.1±210.3.The other six OPEs had no significant bioaccumulation effect,with the BCF being in the range of 6.0±1.2~126.3±9.1.The respiratory rate constant k_u of OPEs in the Koi muscle was calculated by using the first-order kinetic model and the maximum respiratory rate constant was found for TPhP(2.9).Therefore,the rate of TPhP entering the Koi body in the seven OPEs is the fastest.The respiratory rate constants of the other six OPEs were from 0.1 to 1.2.There was no difference of respiratory rate constants of the same species of OPEs in Koi with different exposure concentrations.(4)According to the first-order kinetic model,the maximum discharge rate constant is for TDCPP(0.7),and the discharge rate constants of the other six OPEs are 0.1~0.5.TPhP(0.1)has the lowest discharge rate constant and the longest half-life(6.9 h),indicating that TPhP excreted slowest in Koi.The half-lives of the remaining six OPEs were from 1.0 to 3.5 h.The discharging law of same OPEs under the different exposure concentrations was the same for Koi.There was no significant correlation between the half-life and the octanol-water partition coefficient. |
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