Understanding the distribution, degradation and fate of organophosphate esters in an advanced municipal sewage treatment plant based on mass flow and mass balance analysis

Although organophosphate esters (OPEs) in the ambient environment are from sewage treatment plants due to the discharge of effluent and application of sludge, the distribution, degradation and fate of OPEs in advanced municipal sewage treatment plants remain unclear. This work focused on the use of mass flow and mass balance analysis to understand the behaviors and fate of 14 OPEs in an advanced municipal sewage treatment plant. OPEs were detected in all sewage water and sludge samples with total OPEs (ΣOPEs) concentrations of 1399 ± 263 ng/L in raw sewage aqueous phase, 833 ± 175 ng/L in tertiary effluent aqueous phase, and 315 ± 89 ng/g dry weight in dewatered sludge. The dissolved concentrations of ΣOPEs significantly decreased during biological treatment, whereas negligible decrease was observed in mechanical and physical-chemical treatments. For individual OPE, the chlorinated tris(2-chloroethyl) phosphate (TCEP) and tris(2-chloroisopropyl) phosphate (TCPP) did not decrease but increased during both biological treatment and physical-chemical treatment. Mass flow analysis indicated the total removal efficiency of ΣOPEs in aqueous phase was 40.5%, and the polarity-specific removal efficiencies for individual OPE were positively related to their solid-water partition coefficients (Kd). Furthermore, mass balance results showed that 53.1% and 6.3% of the initial OPE mass flow were eventually transferred to the effluents and dewatered sludge, respectively, while the remaining 39.9% and 0.7% were lost due to biodegradation and physical-chemical treatment, respectively. It was indicated that the activated sludge treatment system with anaerobic/anoxic/aerobic bioreactors was a major factor in the removal of OPEs from the raw sewage, while transfer to dewatered sludge governed by hydrophobic interactions was limited during the sewage treatment. Meanwhile, the degradation difference of OPEs in activated sludge treatment was more related with their molecular structure over their hydrophobicity.