Potential risk of coupling products between tetrahalobisphenol A and humic acid prepared via oxidation with a biomimetic catalyst

Tetrahalobisphenol A (TXPBAs, X = Br or Cl), TBBPA and TCBPA, which are widely used as flame retardants, ultimately disposed of in landfills. In landfills, enzymatically oxidized TXBPAs can be covalently incorporated into humic acids (HAs) to form coupling products (HA-TXBPAs). In the present study, HA-TXBPAs were prepared by catalytic oxidation with iron(III)-phthalocyanine-tetrasulfate as a model of oxidative enzymes. The stability of HA-TXBPAs was evaluated by incubating them under physicochemical conditions of landfills (pH 9 and 50 °C). For HA-TBBPA, 18–26% of TBBPA was released from HA-TBBPA, due to the acid dissociation of the loosely bound TBBPA. However, no additional release was observed, even after 30 days, indicating that 74–82% of the TBBPA was incorporated into the HA. For HA-TCBPA, 3–4% of TCBPA and a major byproduct, 4-(2-hydroxyisopropyl)-2,6-dichlorophenol, was found to be loosely incorporated into HA. For both TBBPA and TCBPA, covalently bound organo-halogens were not released during the 30 days of incubation. Inhibition of the growth of Chlamydomonas reinhardtii was indicated when trace levels of TXBPAs (approximately 0.1 μM) were present. These results suggest that HA-TXBPAs contain not only covalently incorporated TXBPAs but also loosely bound TXBPAs and halophenols. The latter in HA-TXBPAs have the potential to leach from landfills and affect aquatic ecosystems.