Removal of organophosphorus flame retardant by biochar-coated nZVI activating persulfate: Synergistic mechanism of adsorption and catalytic degradation

Triphenyl phosphate (TPhP) is a typical aromatic-based non-chlorinated organophosphorus flame retardant, which has been widely detected in a variety of environments and poses high environmental and human health risks. In this study, biochar coated nano-zero-valent iron (nZVI) was fabricated to activate persulfate (PS) to degrade TPhP from water. A range of biochars (BC400, BC500, BC600, BC700, and BC800) was prepared as potential support to coat nZVI by pyrolyzing corn stalk at 400, 500, 600, 700 and 800 °C. As outperformed other biochars in adsorption rate, adsorption capacity, and less reluctant to be influenced by environmental factors (pH, humic acid (HA), coexistence of anions), BC800 was to act as support to coat nZVI (labeled as BC800@nZVI). SEM, TEM, XRD and XPS characterization showed that nZVI was successfully supported on the BC800. Removal efficiency of 10 mg L-1 TPhP by BC800@nZVI/PS could reach to 96.9% with a high catalytic degradation kinetic rate of 0.0484 min-1 under optimal condition. The removal efficiency remained stable in a wide pH range (3-9) and moderate concentration of HA and coexistence of anions, demonstrated the promising of using BC800@nZVI/PS system to eliminate TPhP contamination. Results from the radical scavenging and electron paramagnetic resonance (EPR) experiments demonstrated radical pathway (i.e. SO4·- and HO·) and non-radical pathway via 1O2 both play important role in TPhP degradation. The TPhP degradation pathway was proposed based on the six degradation intermediates analyzed by LC-MS. This study illustrated the synergistic mechanism of adsorption and catalytic oxidation removal of TPhP by BC800@nZVI/PS system, and provided a cost-efficient approach for TPhP remediation.