Thermally activated persulfate (TAP)-enhanced tris(2-chloroethyl) phosphate removal in real-world waters based on a response-surface approach as well as toxicological evaluation on its degradation products

As a typical organophosphorus flame retardant, tris(2-chloroethyl) phosphate (TCEP) is refractory in aqueous environment. The application of TAP is a promising method for removing pollutants. Herein, the removal of TCEP using TAP was rigorously investigated, and the effects of some key variables were optimized by the one-factor-at-a-time approach. To further evaluate the interactions among variables, the response surface methodology (RSM) based on central composite design was employed. Under optimized conditions (pH 5, [PS] 0 : [TCEP] 0 = 500:1), the maximum removal efficiency (RE) of TCEP reached up to 90.6%. In real-world waters, the RE of TCEP spanned the range of 56%− 65% in river water, pond water, lake water and sanitary sewage. The low-concentration Cl - (0.1 mM) promoted TCEP degradation, but the contrary case occurred when the high-concentration Cl - , NO 3 - , CO 3 2- , HCO 3 - , HPO 4 2- , H 2 PO 4 - , NH 4 + and humic acid were present owing to their prominently quenching effects on SO 4 •- . Both EPR and scavenger experiments revealed that the main radicals in the TAP system were SO 4 •- and •OH, in which SO 4 •- played the most crucial role in TCEP degradation. GC-MS/MS analysis disclosed that two degradation products appeared, sourcing from the replacement, oxidation, hydroxylation and water-molecule elimination reactions. The other two products were inferred from the comprehensive literature. As for acute toxicity to fish, daphnid and green algae, product A displayed the slightly higher toxicity, whereas other three products exhibited the declining toxicity as compared to their parent molecule. These findings offer a theoretical/practical reference for high-efficiency removal of TCEP and its ecotoxicological risk evaluation.