Removal of organophosphate esters from municipal secondary effluent by ozone and UV/H2O2 treatments

• Ozone and UV/H2O2 were applied to remove eight OPEs in three water matrices.
• Chlorinated OPEs and TEHP were more recalcitrant to oxidation than other OPEs.
• HA significantly enhanced the degradation of reactive OPEs in ozone treatment.
• UV/H2O2 was more cost-effective than ozone for the removal of target OPEs.

Organophosphate esters (OPEs) have emerged as a new class of contaminants due to their massive use as flame retardants and plasticizers. These contaminants are toxic to aquatic organisms and some of them are not biodegradable in wastewater treatment plants. This study investigated the degradation kinetics of eight typical OPEs during ozone and UV/H2O2 treatments in Milli-Q water, humic acid (HA) solution, and municipal secondary effluent. The studied OPEs included three chlorinated: tris(2-chloroethyl) phosphate (TCEP), tris(chloropropyl) phosphate (TCPP) and tris(dichloropropyl) phosphate (TDCP); two aromatic: triphenyl phosphate (TPhP) and tricresyl phosphate (TCrP); and three aliphatic: tri-n-butyl phosphate (TnBP), tris(2-butoxyethyl) phosphate (TBEP), and tris(2-ethylhexyl) phosphate (TEHP). Results indicate that the degradation of target OPEs conformed to the pseudo-first-order kinetics and UV/H2O2 was more effective than ozone for their elimination by comparing the overall removal efficiencies and energy consumptions. Two aromatic and two aliphatic OPEs (i.e., TPhP, TCrP, TnBP and TBEP) were effectively degraded by ozone and UV/H2O2 in the test water matrices, while all chlorinated and one aliphatic OPEs (i.e., TCEP, TCPP, TDCP and TEHP) were found to be recalcitrant to oxidation. Moreover, the presence of HA significantly enhanced the degradation of reactive OPEs in ozone treatment.